Ring opening cross-metathesis reaction of cyclic olefins with seed oils and the like

ABSTRACT

This invention relates generally to olefin metathesis, and more particularly relates to the ring-opening, ring insertion cross-metathesis of cyclic olefins with internal olefins such as seed oils and the like. In one embodiment, a method is provided for carrying out a catalytic ring-opening cross-metathesis reaction, comprising contacting at least one olefinic substrate with at least one cyclic olefin as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate. The invention has utility in the fields of catalysis, organic synthesis, and industrial chemistry.

RELATED APPLICATIONS

This application claims priority to U.S. Provisional Application Ser. No. 60/853,300, filed Jul. 12, 2006, the disclosure of which is incorporated herein by reference.

TECHNICAL FIELD

This invention relates generally to olefin metathesis, and more particularly relates to the ring-opening, ring insertion cross-metathesis of cyclic olefins with internal olefins such as seed oils and the like. The invention has utility in the fields of catalysis, organic synthesis, and industrial chemistry.

BACKGROUND

In the past 15 years, ruthenium olefin metathesis catalysts have firmly established olefin metathesis as a versatile and reliable synthetic technique for organic syntheses. The exceptionally wide scope of substrates and functional group tolerance makes olefin metathesis a valuable technique. In this application, the use of olefin cross metathesis to produce alpha-olefins is another example of the usefulness and the robustness of olefin metathesis technology. Compared to traditional synthetic organic techniques, olefin metathesis efficiently produces compounds that are otherwise hard to synthesize. Numerous man hours of research have resulted in the elucidation of many olefin metathesis reactions catalyzed by various transition metal complexes. In particular, certain ruthenium and osmium carbene compounds, known as “Grubbs' catalysts,” have been identified as effective catalysts for olefin metathesis reactions such as, for example, cross-metathesis (CM), ring-closing metathesis (RCM), ring-opening metathesis (ROM), ring opening cross metathesis (ROCM), ring-opening metathesis polymerization (ROMP) or acyclic diene metathesis (ADMET) polymerization.

ROCM is a version of cross metathesis and historically has been underutilized mainly due the difficulty of controlling selectively. ROCM is an intermolecular exchange of a cyclic olefin and an acyclic olefin. In these instances, release of ring strain is the driving force for the reaction to proceed. A review of ROCM is provided by Schrader and Snapper in Handbook of Metathesis, Volume 2: Applications in Organic Synthesis (R. H. Grubbs Ed.), Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim, 2003, pp 205-237.

Early ROCM examples were low yielding reactions with poor selectivities. Even with these shortcomings, ROCM has become an important fixture in metathesis history because ROCM was the key reaction used by Yves Chauvin to propose the currently accepted metathesis mechanism that bears his name, i.e. the Chauvin mechanism. Chauvin proposed the interchange of metal carbenes via a metallocyclobutane ring as an alternative mechanism to the then-accepted pair-wise mechanism for olefin cross metathesis. The metallocyclobutane mechanism was proposed based on the ROCM of cyclopentene with 2-pentene, shown in Scheme 1, which resulted in a statistical product distribution (1:2:1 of compounds 1, 2, and 3 respectively). In the pair-wise mechanism only compound 2 would be expected to form, at low conversions. Chauvin was rewarded for his insight and contributions to metathesis by sharing the 2005 Nobel Prize in Chemistry with Dr. Robert Grubbs and Dr. Richard Schrock.

ROCM reactions using cyclododecene and methyl oleate or oleyl acetate have been reported. The reactions employed an ill-defined tungsten catalyst system to produce the ring inserted product, as shown in Scheme 2.

There is an ongoing need in the art for methods and systems that would allow ring insertion cross metathesis of cyclic olefins into internal olefins, e.g., seed oils and the like. This type of reaction would be useful in the preparation of various useful products, including, by way of example, chain-extended trialkylglycerides (TAGs) and chain-extended fatty acid methyl esters (FAMEs). An ideal such reaction could be implemented in the preparation of metathesis products useful as binders in urethane foams, latex pains, printing inks, and high melting point waxes.

SUMMARY OF THE DISCLOSURE

Accordingly, the invention is directed to addressing one or more of the aforementioned issues, and, in one embodiment, provides a method for carrying out a catalytic ring-opening cross-metathesis reaction. The method comprises contacting at least one olefinic substrate with at least one cyclic olefin as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The contacting is carried out under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate.

In another embodiment, the invention provides a method for manufacturing a wax. The method comprises contacting at least one olefinic substrate with at least one cyclic olefin as a cross metathesis partner in the presence of a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from: (i) an unsaturated fatty acid or derivative thereof; (ii) an unsaturated fatty alcohol or derivative thereof; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The reaction is carried out under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate to provide an olefinic product. The method further comprises optionally hydrogenating the olefinic product, wherein the hydrogenation may be partial or complete hydrogenation.

In a still further embodiment, the invention provides a method for carrying out a catalytic ring-opening cross-metathesis reaction. The method comprises contacting at least one olefinic substrate with at least one cyclic olefin functionalized with a functional group as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The contacting is carried out under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate.

In a still further embodiment, the invention provides a method for carrying our a catalytic ring-opening cross metathesis reaction. The method comprises contacting at least one olefinic substrate with at least one cyclic olefin as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst. The catalyst is present in an amount that is less than 1000 ppm relative to the olefinic substrate, and the at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol.

In a further embodiment, the invention provides a reaction system for carrying out a catalytic ring-opening cross-metathesis reaction comprising at least one olefinic substrate, at least one cyclic olefin, and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol.

In a still further embodiment, the invention provides a reaction system for manufacturing a wax. The reaction system comprises at least one olefinic substrate, at least one cyclic olefin, and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol.

In a still further embodiment, the invention provides a ring-opening cross-metathesis product prepared using any of the methods and reaction systems disclosed herein.

In a still further embodiment, the invention provides a chain-extended olefinic substrate formed by a catalytic ring-opening cross-metathesis reaction. The reaction comprises contacting: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol, with (b) at least one cyclic olefin as a cross metathesis partner, in the presence of (c) a ruthenium alkylidene olefin metathesis catalyst, under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate to form the chain-extended olefinic substrate.

In a still further embodiment, the invention provides a kit of parts for carrying out a catalytic ring-opening cross metathesis reaction. The kit of parts comprises at least one olefinic substrate and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The kit of parts further comprises: (a) at least one cyclic olefin; or (b) instructions for adding a cyclic olefin to the at least one olefinic substrate.

In a still further embodiment, the invention provides a kit of parts for manufacturing a wax. The kit of parts comprises at least one olefinic substrate and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The kit of parts further comprises: (a) at least one cyclic olefin; or (b) instructions for adding a cyclic olefin to the at least one olefinic substrate. The kit of parts further comprises instructions for hydrogenating metathesis products.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a typical GC-MS chromatogram of ROCM (n=1) products.

FIG. 2 is a MALDI-TOF spectrum of ROCM Product (n=1) from metathesis of 9C18 and COE

DETAILED DESCRIPTION OF THE DISCLOSURE Terminology and Definitions

Unless otherwise indicated, the invention is not limited to specific reactants, substituents, catalysts, reaction conditions, or the like, as such may vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting.

As used in the specification and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “an α-olefin” includes a single α-olefin as well as a combination or mixture of two or more α-olefin, reference to “a substituent” encompasses a single substituent as well as two or more substituents, and the like.

As used in the specification and the appended claims, the terms “for example,” “for instance,” “such as,” or “including” are meant to introduce examples that further clarify more general subject matter. Unless otherwise specified, these examples are provided only as an aid for understanding the invention, and are not meant to be limiting in any fashion.

In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings:

The term “alkyl” as used herein refers to a linear, branched, or cyclic saturated hydrocarbon group typically although not necessarily containing 1 to about 24 carbon atoms, preferably 1 to about 12 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, octyl, decyl, and the like, as well as cycloalkyl groups such as cyclopentyl, cyclohexyl and the like. Generally, although again not necessarily, alkyl groups herein contain 1 to about 12 carbon atoms. The term “lower alkyl” intends an alkyl group of 1 to 6 carbon atoms, and the specific term “cycloalkyl” intends a cyclic alkyl group, typically having 4 to 8, preferably 5 to 7, carbon atoms. The term “substituted alkyl” refers to alkyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkyl” and “heteroalkyl” refer to alkyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkyl” and “lower alkyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkyl and lower alkyl, respectively.

The term “alkylene” as used herein refers to a difunctional linear, branched, or cyclic alkyl group, where “alkyl” is as defined above.

The term “alkenyl” as used herein refers to a linear, branched, or cyclic hydrocarbon group of 2 to about 24 carbon atoms containing at least one double bond, such as ethenyl, n-propenyl, isopropenyl, n-butenyl, isobutenyl, octenyl, decenyl, tetradecenyl, hexadecenyl, eicosenyl, tetracosenyl, and the like. Preferred alkenyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkenyl” intends an alkenyl group of 2 to 6 carbon atoms, and the specific term “cycloalkenyl” intends a cyclic alkenyl group, preferably having 5 to 8 carbon atoms. The term “substituted alkenyl” refers to alkenyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkenyl” and “heteroalkenyl” refer to alkenyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkenyl” and “lower alkenyl” include linear, branched, cyclic, unsubstituted, substituted, and/or heteroatom-containing alkenyl and lower alkenyl, respectively.

The term “alkenylene” as used herein refers to a difunctional linear, branched, or cyclic alkenyl group, where “alkenyl” is as defined above.

The term “alkynyl” as used herein refers to a linear or branched hydrocarbon group of 2 to about 24 carbon atoms containing at least one triple bond, such as ethynyl, n-propynyl, and the like. Preferred alkynyl groups herein contain 2 to about 12 carbon atoms. The term “lower alkynyl” intends an alkynyl group of 2 to 6 carbon atoms. The term “substituted alkynyl” refers to alkynyl substituted with one or more substituent groups, and the terms “heteroatom-containing alkynyl” and “heteroalkynyl” refer to alkynyl in which at least one carbon atom is replaced with a heteroatom. If not otherwise indicated, the terms “alkynyl” and “lower alkynyl” include linear, branched, unsubstituted, substituted, and/or heteroatom-containing alkynyl and lower alkynyl, respectively.

The term “alkoxy” as used herein intends an alkyl group bound through a single, terminal ether linkage; that is, an “alkoxy” group may be represented as —O-alkyl where alkyl is as defined above. A “lower alkoxy” group intends an alkoxy group containing 1 to 6 carbon atoms. Analogously, “alkenyloxy” and “lower alkenyloxy” respectively refer to an alkenyl and lower alkenyl group bound through a single, terminal ether linkage, and “alkynyloxy” and “lower alkynyloxy” respectively refer to an alkynyl and lower alkynyl group bound through a single, terminal ether linkage.

The term “aryl” as used herein, and unless otherwise specified, refers to an aromatic substituent containing a single aromatic ring or multiple aromatic rings that are fused together, directly linked, or indirectly linked (such that the different aromatic rings are bound to a common group such as a methylene or ethylene moiety). Preferred aryl groups contain 5 to 24 carbon atoms, and particularly preferred aryl groups contain 5 to 14 carbon atoms. Exemplary aryl groups contain one aromatic ring or two fused or linked aromatic rings, e.g., phenyl, naphthyl, biphenyl, diphenylether, diphenylamine, benzophenone, and the like. “Substituted aryl” refers to an aryl moiety substituted with one or more substituent groups, and the terms “heteroatom-containing aryl” and “heteroaryl” refer to aryl substituents in which at least one carbon atom is replaced with a heteroatom, as will be described in further detail infra.

The term “aryloxy” as used herein refers to an aryl group bound through a single, terminal ether linkage, wherein “aryl” is as defined above. An “aryloxy” group may be represented as —O-aryl where aryl is as defined above. Preferred aryloxy groups contain 5 to 24 carbon atoms, and particularly preferred aryloxy groups contain 5 to 14 carbon atoms. Examples of aryloxy groups include, without limitation, phenoxy, o-halo-phenoxy, m-halo-phenoxy, p-halo-phenoxy, o-methoxy-phenoxy, m-methoxy-phenoxy, p-methoxy-phenoxy, 2,4-dimethoxy-phenoxy, 3,4,5-trimethoxy-phenoxy, and the like.

The term “alkaryl” refers to an aryl group with an alkyl substituent, and the term “aralkyl” refers to an alkyl group with an aryl substituent, wherein “aryl” and “alkyl” are as defined above. Preferred alkaryl and aralkyl groups contain 6 to 24 carbon atoms, and particularly preferred alkaryl and aralkyl groups contain 6 to 16 carbon atoms. Alkaryl groups include, for example, p-methylphenyl, 2,4-dimethylphenyl, p-cyclohexylphenyl, 2,7-dimethylnaphthyl, 7-cyclooctylnaphthyl, 3-ethyl-cyclopenta-1,4-diene, and the like. Examples of aralkyl groups include, without limitation, benzyl, 2-phenyl-ethyl, 3-phenyl-propyl, 4-phenyl-butyl, 5-phenyl-pentyl, 4-phenylcyclohexyl, 4-benzylcyclohexyl, 4-phenylcyclohexylmethyl, 4-benzylcyclohexylmethyl, and the like. The terms “alkaryloxy” and “aralkyloxy” refer to substituents of the formula —OR wherein R is alkaryl or aralkyl, respectively, as just defined.

The term “acyl” refers to substituents having the formula —(CO)-alkyl, —(CO)-aryl, or —(CO)-aralkyl, and the term “acyloxy” refers to substituents having the formula —O(CO)-alkyl, —O(CO)-aryl, or —O(CO)-aralkyl, wherein “alkyl,” “aryl, and “aralkyl” are as defined above.

The terms “cyclic” and “ring” refer to alicyclic or aromatic groups that may or may not be substituted and/or heteroatom containing, and that may be monocyclic, bicyclic, or polycyclic. The term “alicyclic” is used in the conventional sense to refer to an aliphatic cyclic moiety, as opposed to an aromatic cyclic moiety, and may be monocyclic, bicyclic, or polycyclic.

The terms “halo” and “halogen” are used in the conventional sense to refer to a chloro, bromo, fluoro, or iodo substituent.

“Hydrocarbyl” refers to univalent hydrocarbyl radicals containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated, and unsaturated species, such as alkyl groups, alkenyl groups, aryl groups, and the like. The term “lower hydrocarbyl” intends a hydrocarbyl group of 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, and the term “hydrocarbylene” intends a divalent hydrocarbyl moiety containing 1 to about 30 carbon atoms, preferably 1 to about 24 carbon atoms, most preferably 1 to about 12 carbon atoms, including linear, branched, cyclic, saturated and unsaturated species. The term “lower hydrocarbylene” intends a hydrocarbylene group of 1 to 6 carbon atoms. “Substituted hydrocarbyl” refers to hydrocarbyl substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbyl” and “heterohydrocarbyl” refer to hydrocarbyl in which at least one carbon atom is replaced with a heteroatom. Similarly, “substituted hydrocarbylene” refers to hydrocarbylene substituted with one or more substituent groups, and the terms “heteroatom-containing hydrocarbylene” and heterohydrocarbylene” refer to hydrocarbylene in which at least one carbon atom is replaced with a heteroatom. Unless otherwise indicated, the term “hydrocarbyl” and “hydrocarbylene” are to be interpreted as including substituted and/or heteroatom-containing hydrocarbyl and hydrocarbylene moieties, respectively.

The term “heteroatom-containing” as in a “heteroatom-containing hydrocarbyl group” refers to a hydrocarbon molecule or a hydrocarbyl molecular fragment in which one or more carbon atoms is replaced with an atom other than carbon, e.g., nitrogen, oxygen, sulfur, phosphorus or silicon, typically nitrogen, oxygen or sulfur. Similarly, the term “heteroalkyl” refers to an alkyl substituent that is heteroatom-containing, the term “heterocyclic” refers to a cyclic substituent that is heteroatom-containing, the terms “heteroaryl” and heteroaromatic” respectively refer to “aryl” and “aromatic” substituents that are heteroatom-containing, and the like. It should be noted that a “heterocyclic” group or compound may or may not be aromatic, and further that “heterocycles” may be monocyclic, bicyclic, or polycyclic as described above with respect to the term “aryl.” Examples of heteroalkyl groups include alkoxyaryl, alkylsulfanyl-substituted alkyl, N-alkylated amino alkyl, and the like. Examples of heteroaryl substituents include pyrrolyl, pyrrolidinyl, pyridinyl, quinolinyl, indolyl, pyrimidinyl, imidazolyl, 1,2,4-triazolyl, tetrazolyl, etc., and examples of heteroatom-containing alicyclic groups are pyrrolidino, morpholino, piperazino, piperidino, etc.

By “substituted” as in “substituted hydrocarbyl,” “substituted alkyl,” “substituted aryl,” and the like, as alluded to in some of the aforementioned definitions, is meant that in the hydrocarbyl, alkyl, aryl, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more non-hydrogen substituents. Examples of such substituents include, without limitation: functional groups referred to herein as “Fn,” such as halo, hydroxyl, sulfhydryl, C₁-C₂₄ alkoxy, C₂-C₂₄ alkenyloxy, C₂-C₂₄ alkynyloxy, C₅-C₂₄ aryloxy, C₆-C₂₄ aralkyloxy, C₆-C₂₄ alkaryloxy, acyl (including C₂-C₂₄ alkylcarbonyl (—CO-alkyl) and C₆-C₂₄ arylcarbonyl (—CO-aryl)), acyloxy (—O-acyl, including C₂-C₂₄ alkylcarbonyloxy (—O—CO-alkyl) and C₆-C₂₄ arylcarbonyloxy (—O—CO-aryl)), C₂-C₂₄ alkoxycarbonyl (—(CO)—O-alkyl), C₆-C₂₄ aryloxycarbonyl (—(CO)—O-aryl), halocarbonyl (—CO)—X where X is halo), C₂-C₂₄ alkylcarbonato (—O—(CO)—O-alkyl), C₆-C₂₄ arylcarbonato (—O—(CO)—O-aryl), carboxy (—COOH), carboxylato (—COO⁻), carbamoyl (—(CO)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted carbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted carbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, thiocarbamoyl (—(CS)—NH₂), mono-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CO)—NH(C₁-C₂₄ alkyl)), di-(C₁-C₂₄ alkyl)-substituted thiocarbamoyl (—(CO)—N(C₁-C₂₄ alkyl)₂), mono-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CO)—NH-aryl), di-(C₅-C₂₄ aryl)-substituted thiocarbamoyl (—(CO)—N(C₅-C₂₄ aryl)₂), di-N—(C₁-C₂₄ alkyl), N—(C₅-C₂₄ aryl)-substituted thiocarbamoyl, carbamido (—NH—(CO)—NH₂), cyano(—CEN), cyanato (—O—C—N), thiocyanato (—S—C—N), formyl (—(CO)—H), thioformyl (—(CS)—H), amino (—NH₂), mono-(C₁-C₂₄ alkyl)-substituted amino, di-(C₁-C₂₄ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₄ alkylamido (—NH—(CO)-alkyl), C₆-C₂₄ arylamido (—NH—(CO)-aryl), imino (—CR═NH where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), C₂-C₂₀ alkylimino (—CR═N(alkyl), where R=hydrogen, C₁-C₂₄ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), arylimino (—CR═N(aryl), where R=hydrogen, C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), nitro (—NO₂), nitroso (—NO), sulfo (—SO₂—OH), sulfonato (—SO₂—O—), C₁-C₂₄ alkylsulfanyl (—S-alkyl; also termed “alkylthio”), C₅-C₂₄ arylsulfanyl (—S-aryl; also termed “arylthio”), C₁-C₂₄ alkylsulfinyl (—(SO)-alkyl), C₅-C₂₄ arylsulfinyl (—(SO)-aryl), C₁-C₂₄ alkylsulfonyl (—SO₂-alkyl), C₅-C₂₄ arylsulfonyl (—SO₂-aryl), boryl (—BH₂), borono (—B(OH)₂), boronato (—B(OR)₂ where R is alkyl or other hydrocarbyl), phosphono (—P(O)(OH)₂), phosphonato (—P(O)(O—)₂), phosphinato (—P(O)(O—)), phospho (—PO₂), and phosphino (—PH₂); and the hydrocarbyl moieties C₁-C₂₄ alkyl (preferably C₁-C₁₂ alkyl, more preferably C₁-C₆ alkyl), C₂-C₂₄ alkenyl (preferably C₂-C₁₂ alkenyl, more preferably C₂-C₆ alkenyl), C₂-C₂₄ alkynyl (preferably C₂-C₁₂ alkynyl, more preferably C₂-C₆ alkynyl), C₅-C₂₄ aryl (preferably C₅-C₁₄ aryl), C₆-C₂₄ alkaryl (preferably C₆-C₁₆ alkaryl), and C₆-C₂₄ aralkyl (preferably C₆-C₁₆ aralkyl).

By “functionalized” as in “functionalized hydrocarbyl,” “functionalized alkyl,” “functionalized olefin,” “functionalized cyclic olefin,” and the like, is meant that in the hydrocarbyl, alkyl, olefin, cyclic olefin, or other moiety, at least one hydrogen atom bound to a carbon (or other) atom is replaced with one or more functional groups such as those described hereinabove.

In addition, the aforementioned functional groups may, if a particular group permits, be further substituted with one or more additional functional groups or with one or more hydrocarbyl moieties such as those specifically enumerated above. Analogously, the above-mentioned hydrocarbyl moieties may be further substituted with one or more functional groups or additional hydrocarbyl moieties such as those specifically enumerated.

“Optional” or “optionally” means that the subsequently described circumstance may or may not occur, so that the description includes instances where the circumstance occurs and instances where it does not. For example, the phrase “optionally substituted” means that a non-hydrogen substituent may or may not be present on a given atom, and, thus, the description includes structures wherein a non-hydrogen substituent is present and structures wherein a non-hydrogen substituent is not present.

A “kit of parts,” as used herein, refers to a packaged collection of related components. Unless otherwise specified, the components of a kit of parts may be packaged individually or together in any combination.

A “reaction system,” as used herein, refers to a functionally related group of components.

Methods and Compositions of the Disclosure

I. FIRST EMBODIMENT Ring-Opening, Ring Insertion Cross-Metathesis Method of a Cyclic Olefin and an Internal Olefin as an Olefinic Substrate

In a first embodiment, the invention provides an olefin cross-metathesis method in which the method involves ring-opening, ring insertion metathesis of at least one olefinic substrate and at least one cyclic olefin as the cross metathesis partner. The olefinic substrate is selected from (i) an unsaturated fatty acid or derivative thereof, (ii) an unsaturated fatty alcohol or derivative thereof, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. It will be appreciated that esterification products of an unsaturated fatty acid with an alcohol include many commercially available and industrially significant compositions, e.g., monoglycerides, diglycerides, and triglycerides such as may be found in seed oils and the like. The reaction is carried out catalytically, generally in the presence of a ruthenium alkylidene metathesis catalyst. In this embodiment, the reaction is carried out by contacting the at least one olefinic substrate with the cross metathesis partner, i.e., the at least one cyclic olefin, in the presence of the metathesis catalyst under reaction conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate.

The olefinic substrate is any olefinic substrate that is suitable for the metathesis methods disclosed herein and that is selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The olefinic substrate may also be a mixture of compounds.

Fatty acids are organic compounds comprising a hydrophobic carbon chain substituted with an acid moiety at one end. The hydrophobic portion is a carbon chain that typically contains at least six carbon atoms, and may contain up to 20 or more carbon atoms in the chain. The hydrophobic carbon chain may be substituted or unsubstituted, may contain one or more heteroatoms such as N, O, S or P, may contain one or more functional groups such as those described hereinabove, and may contain one or more unsaturated regions (e.g., carbon-carbon double bonds or triple bonds). The substituents on the hydrophobic carbon chain may be any of the substituents described hereinabove. The hydrophobic carbon chain contains an acid moiety at one end, and the acid moiety is typically a carboxylic acid. The carboxylic acid moiety may be ionized, such that it is in the form of a salt (e.g., a sodium or potassium salt). The carboxylic acid may also be derivitized using any of the derivitization methods typically employed for carboxylic acid compounds. For example, the carboxylic acid may be esterified via an esterification reaction with an alcohol. Any alcohol suitable for esterification with the fatty acid may be employed. The alcohol may be saturated or unsaturated, and may be monohydric, dihydric, or polyhydric. The alcohol may be a C₁-C₂₀ alcohol that optionally contains one or more heteroatoms, and optionally contains one or more substituents. The alcohol may optionally be cyclic and/or branched. Examples of alcohols suitable for preparing esters from the fatty acids disclosed herein include methanol, ethanol, propanol (e.g., isopropanol), butanol, 1,2-dihydroxypropane, and glycerol.

Fatty alcohols are organic compounds comprising a hydrophobic carbon chain substituted with an alcohol moiety (i.e., —OH) at one end. The hydrophobic carbon chain is as described for fatty acids hereinabove. As with fatty acids, the alcohol moiety may be ionized, such that it is in the form of a salt (e.g., a sodium or potassium salt). Also as with fatty acids, the alcohol may be derivatized using any derivatization methods employed for alcohols. For example, the alcohol may be converted to an ether via reaction with a compound containing another alcohol, or may be converted to an ester via reaction with a compound containing a carboxylic acid. Any alcohol or ester suitable for derivatizing the fatty alcohol may be employed. Such alcohols and esters include C₁-C₂₀ alcohol and esters that optionally contain one or more heteroatoms, and optionally contain one or more substituents. The alcohols and esters may optionally be cyclic and/or branched. Examples of alcohols and esters suitable for derivatizing the fatty alcohols disclosed herein include methanol and acetic acid.

The fatty acids and fatty alcohols suitable for use as the olefinic substrate in the methods disclosed herein are unsaturated fatty acids or fatty acid derivatives and unsaturated fatty alcohols or fatty alcohol derivatives. That is, the olefinic substrate comprises at least one unsaturated moiety. In one embodiment of the invention, the hydrophobic carbon chain of the fatty acid or fatty alcohol comprises at least one unsaturated moiety. In another embodiment of the invention, the olefinic substrate comprises a saturated fatty acid that is derivatized with an unsaturated compound, or the olefinic substrate comprises a saturated fatty alcohol that is derivitized with an unsaturated compound. For example, a saturated fatty acid may be esterified using an unsaturated alcohol.

Preferred unsaturated moieties are internal olefins. By “internal olefin” is meant an olefin wherein each of the olefinic carbons is substituted by at least one non-hydrogen substituent. The non-hydrogen substituents are selected from hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. The internal olefin is therefore at least disubstituted, and may further include additional non-hydrogen substituents (e.g., a trisubstituted internal olefin). Each of the substituents on the internal olefinic carbons may be further substituted as described supra. The internal olefin may be in the Z- or E-configuration. When the olefinic substrate comprises a plurality of internal olefins, the olefinic substrate may comprise a mixture of internal olefins (varying in stereochemistry and/or substituent identity), or may comprise a plurality of identical internal olefins.

In general, the olefinic substrate may be represented by the formula (R^(I))(R^(II))C═C(R^(III))(R^(IV)), wherein R^(I), R^(II), R^(III), and R^(IV) are independently selected from H, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, provided that at least one of R^(I) or R^(II) and at least one of R^(III) or R^(IV) is other than H. In a preferred embodiment, either R^(I) or R^(II) and either R^(III) or R^(IV) is H, such that the internal olefin is di-substituted.

In a preferred embodiment, the olefinic substrate is a derivative of glycerol, and has the structure of formula (I)

wherein R^(V), R^(VI), and R^(VII) are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, provided that at least one of R^(V), R^(VI), and R^(VII) is other than hydrogen and comprises an internal olefin.

As an example, the olefinic substrate is a “glyceride,” and comprises glycerol esterified with 1, 2, or 3 fatty acids, such that the olefinic substrate is a monoacylglycerol, diacylglycerol, or triacylglycerol (i.e., a monoglyceride, diglyceride, or triglyceride, respectively). The olefinic substrate may also be a mixture of glycerides. Each fatty acid-derived fragment of the olefinic substrate may independently be saturated, monounsaturated, or polyunsaturated, and may furthermore derive (or be derivable) from naturally-occurring fatty acids or from synthetic fatty acids. Thus, the glyceride may be a compound with the structure of formula (I), wherein R^(V), R^(VI), or R^(VII), or a combination thereof, is —C(═O)—R^(VIII), wherein R^(VIII), is hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarby, or substituted heteroatom-containing hydrocarbyl, provided that at least one of R^(V), R^(VI), and R^(VII) contains an unsaturated moiety. As a further example, the olefinic substrate may comprise glycerol esterified with one, two, or three fatty acids that are independently selected from palmitoleic acid, vaccenic acid, erucic acid, oleic acid, alpha-linolenic acid, gamma-linolenic acid, linoleic acid, gadoleic acid, arachidonic acid, docosahexaenoic acid (i.e., DHA), eicosapentaenoic acid (i.e., EPA), and CH₃(CH₂)_(n)COOH, where n is 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, or 22.

The olefinic substrate may be solid (e.g., a fat) or liquid (e.g., an oil). Preferred glycerides that may be used as the olefinic substrate are seed oils and/or other vegetable oils, or are compounds that derive from seed oils and/or vegetable oils. Preferred oil sources include soybean oil, sunflower oil, canola oil, safflower oil, cottonseed oil, castor oil, rapeseed oil, peanut oil, corn oil, olive oil, palm oil, sesame oil, palm kernel oil, meadowfoam oil, grape seed oil, phospholipids, phosphoglycerides, phosphatidyl ethanolamine, phosphatidyl choline, ceramides, and sphingolipids. Further preferred oils include seed oil esters, such as jojoba oil and oils from animal sources such as fish oil, butterfat, lard, tallow, chicken fat, goose fat, menhaden oil, cod liver oil, herring oil, seal oil, shark oil, and whale oil.

The olefinic substrate may be a compound or mixture of compounds that is derived from a glyceride using any one or combination of methods well known in the chemical arts. Such methods include saponification, esterification, hydrogenation, isomerization, oxidation, and reduction. For example, the olefinic substrate may the carboxylic acid or mixture of carboxylic acids that result from the saponification of a monoacylglycerol, diacylglycerol, triacylglycerol, or mixture thereof. In a preferred embodiment, the olefinic substrate is a fatty acid methyl ester (FAME), i.e., the methyl ester of a carboxylic acid that is derived from a glyceride. Sunflower FAME, safflower FAME, soy FAME (i.e., methyl soyate), and canola FAME are examples of such olefinic substrates. Additionally, olefinic substrates may include derivatives of fatty acids such as oleamides, linoleamides, linolenamides, erucamide and substitution of the nitrogen with any combination of hydrogen, alkyl and aryl groups.

In addition, preferred olefinic substrates include seed oil-derived compounds such as methyl oleate.

Preferred fatty alcohol derivatives include oleyl chloride (ie 9-octadecenyl chloride), oleyl bromide, oleyl iodide, oleyl fluoride, linoleyl chloride (ie 9,12-octadecadienyl chloride), linoleyl bromide, linoleyl iodide, linoleyl fluoride, linolenyl chloride (ie 9,12,15-octadecatrienyl chloride), linolenyl bromide, linolenyl iodide, linolenyl fluoride, oleyl amine, linoleyl amine, linolenyl amine, oleyl thiol, linoleyl thiol, linolenyl thiol, oleyl phosphine, linoleyl phosphine, linolenyl phosphine.

In addition to the olefinic substrate, described hereinabove, the metathesis reactions disclosed herein involve a cross-metathesis partner. Preferred cross-metathesis partners include cyclic olefins, and any cyclic olefin suitable for the metathesis reactions disclosed herein may be used. Preferred cyclic olefins include optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄ hydrocarbons that may be mono-, di- or poly-cyclic. The cyclic olefin may be stained or unstrained.

Preferred cyclic olefins include C₅ to C₂₄ unsaturated hydrocarbons. Also preferred are C₅ to C₂₄ cyclic hydrocarbons that contain one or more (typically 2 to 12) heteroatoms such as O, N, S, or P. For example, crown ether cyclic olefins may include numerous 0 heteroatoms throughout the cycle, and these are within the scope of the invention. In addition, preferred cyclic olefins are C₅ to C₂₄ hydrocarbons that contain one or more (typically 2 or 3) olefins. For example, the cyclic olefin may be mono-, di-, or tri-unsaturated. Examples of cyclic olefins include cyclooctene, cyclododecene, and (c,t,t)-1,5,9-cyclododecatriene.

The cyclic olefins may also comprise multiple (typically 2 or 3) rings. For example, the cyclic olefin may be mono-, di-, or tri-cyclic. When the cyclic olefin comprises more than one ring, the rings may or may not be fused. Examples of cyclic olefins that comprise multiple rings include norbornene, dicyclopentadiene, and 5-ethylidene-2-norbornene.

The cyclic olefin may also be substituted—for example, a C₅ to C₂₄ cyclic hydrocarbon wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with non-hydrogen substituents. Suitable non-hydrogen substituents may be chosen from the substituents described hereinabove. For example, functionalized cyclic olefins, i.e., C₅ to C₂₄ cyclic hydrocarbons wherein one or more (typically 2, 3, 4, or 5) of the hydrogens are replaced with functional groups, are within the scope of the invention. Suitable functional groups may be chosen from the functional groups described hereinabove. For example, a cyclic olefin functionalized with an alcohol group may be used to prepare a ring-insertion product comprising pendent alcohol groups. Functional groups on the cyclic olefin may be protected in cases where the functional group interferes with the metathesis catalyst, and any of the protecting groups commonly used in the art may be employed. Acceptable protecting groups may be found, for example, in Greene et al., Protective Groups in Organic Synthesis, 3^(rd) Ed. (New York: Wiley, 1999). Examples of functionalized cyclic olefins include 2-hydroxymethyl-5-norbornene, 2-[(2-hydroxyethyl)carboxylate]-5-norbornene, Cyclecanol, 5-n-hexyl-2-norbornene, 5-n-butyl-2-norbornene.

Cyclic olefins incorporating any combination of the abovementioned features (i.e., heteroatoms, substituents, multiple olefins, multiple rings) are suitable for the methods disclosed herein.

The cyclic olefins useful in the methods disclosed herein may be strained or unstrained. It will be appreciated that the amount of ring strain varies for each compound, and depends upon a number of factors including the size of the ring, the presence and identity of substituents, and the presence of multiple rings. Ring strain is one factor in determining the reactivity of a molecule towards ring-opening olefin metathesis reactions. Highly strained cyclic olefins, such as certain bicyclic compounds, readily undergo ring opening reactions with olefin metathesis catalysts. Less strained cyclic olefins, such as certain unsubstituted hydrocarbon monocyclic olefins, are generally less reactive to such reactions. It should be noted, however, that in some cases, ring opening reactions of relatively unstrained (and therefore relatively unreactive) cyclic olefins becomes possible when performed in the presence of the olefinic substrates disclosed herein.

A plurality of cyclic olefins may be used as the cross-metathesis partner with the olefinic substrate. For example, two cyclic olefins selected from the cyclic olefins described hereinabove may be employed in order to form metathesis products that incorporate both cyclic olefins. Where two or more cyclic olefins are used, one example of a preferred second cyclic olefin is a cyclic alkenol, i.e., a C₅-C₂₄ cyclic hydrocarbon wherein at least one of the hydrogen substituents is replaced with an alcohol or protected alcohol moiety to yield a functionalized cyclic olefin.

The use of a plurality of cyclic olefins, and in particular when at least one of the cyclic olefins is functionalized, allows for further control over the positioning of functional groups within the products. For example, the density of cross-linking points can be controlled in polymers and macromonomers prepared using the methods disclosed herein. Control over the quantity and density of substituents and functional groups also allows for control over the physical properties (e.g., melting point, tensile strength, glass transition temperature, etc.) of the products. Control over these and other properties is possible for reactions using only a single cyclic olefin, but it will be appreciated that the use of a plurality of cyclic olefins further enhances the range of possible metathesis products.

A ring insertion reaction is carried out by contacting the at least one olefinic substrate with the cross metathesis partner, i.e., the at least one cyclic olefin, in the presence of the metathesis catalyst under reaction conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate. Examples are illustrated in Schemes 3, 4, and 5 in which an olefinic substrate is reacted with a cyclic olefin to produce metathesis products.

In Scheme 3 and Scheme 4, the ring insertion cross metathesis reactions are carried out using seed oils as the olefinic substrates to produce chain extended trialkylglycerides (TAGs) and chain extended fatty acid methyl esters (FAMEs). The metathesis products shall, however, not be limited to these specific products and can include any mixtures of chain extended fatty acid components, mixtures of chain extended olefin components, and mixtures of chain extended diacid components.

An illustration of a ring opening cross metathesis reaction in which a cycloalkene and a cyclic alkenol are employed is provided in Scheme 5. The product from the reaction shown in scheme 5 is a copolymer that contains pendent alcohol groups dispersed throughout the backbone. It will be appreciated that the spacing between alcohol groups along the product polymer backbone will be dependent upon the relative amounts of cyclic olefin and cyclic alkenol that are incorporated into the polymer. Therefore, relative amounts of cyclic olefin and cyclic alkenol added to the reaction mixture is one way in which this spacing can be controlled.

The reactions disclosed herein are catalyzed by any of the metathesis catalysts that are described infra. The catalyst is typically added to the reaction medium as a solid, but may also be added as a solution wherein the catalyst is dissolved in an appropriate solvent, or as a suspension wherein the catalyst is suspended in an appropriate liquid. It will be appreciated that the amount of catalyst that is used (i.e., the “catalyst loading”) in the reaction is dependent upon a variety of factors such as the identity of the reactants and the reaction conditions that are employed. It is therefore understood that catalyst loading may be optimally and independently chosen for each reaction. In general, however, the catalyst will be present in an amount that ranges from a low of about 0.1 ppm, 1 ppm, or 5 ppm, to a high of about 10 ppm, 15 ppm, 25 ppm, 50 ppm, 100 ppm, 200 ppm, 500 ppm, or 1000 ppm relative to the amount of the olefinic substrate. Catalyst loading, when measured in ppm relative to the amount of the olefinic substrate, is calculated using the equation ${{ppm}\quad{catalyst}} = {\frac{{moles}\quad{catalyst}}{{moles}\quad{olefinic}\quad{substrate}}*1\text{,}000\text{,}000.}$ Alternatively, the amount of catalyst can be measured in terms of mol % relative to the amount of olefinic substrate, using the equation ${{mol}\quad\%\quad{catalyst}} = {\frac{{moles}\quad{catalyst}}{{moles}\quad{olefinic}\quad{substrate}}*100.}$ Thus, the catalyst will generally be present in an amount that ranges from a low of about 0.00001 mol %, 0.0001 mol %, or 0.0005 mol %, to a high of about 0.001 mol %, 0.0015 mol %, 0.0025 mol %, 0.005 mol %, 0.01 mol %, 0.02 mol %, 0.05 mol %, or 0.1 mol % relative to the olefinic substrate.

In a preferred embodiment, the reactions disclosed herein are carried out under a dry, inert atmosphere. Such an atmosphere may be created using any inert gas, including such gases as nitrogen and argon. The use of an inert atmosphere is optimal in terms of promoting catalyst activity, and reactions performed under an inert atmosphere typically are performed with relatively low catalyst loading. The reactions disclosed herein may also be carried out in an oxygen-containing and/or a water-containing atmosphere, and in one embodiment, the reactions are carried out under ambient conditions. The presence of oxygen or water in the reaction may, however, necessitate the use of higher catalyst loadings as compared with reactions performed under an inert atmosphere.

Where the vapor pressure of the reactants allows, the reactions disclosed herein may also be carried out under reduced pressure.

The olefin metathesis catalyst for carrying out the reactions disclosed herein is preferably a Group 8 transition metal complex having the structure of formula (II)

in which the various substituents are as follows.

M is a Group 8 transition metal;

L¹, L² and L³ are neutral electron donor ligands;

n is 0 or 1, such that L³ may or may not be present;

m is 0, 1, or 2;

X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups,

wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together to form one or more cyclic groups, and further wherein any one or more of X¹, X², L¹, L², L³, R¹, and R² may be attached to a support.

Preferred catalysts contain Ru or Os as the Group 8 transition metal, with Ru particularly preferred.

Numerous embodiments of the catalysts useful in the reactions disclosed herein are described in more detail infra. For the sake of convenience, the catalysts are described in groups, but it should be emphasized that these groups are not meant to be limiting in any way. That is, any of the catalysts useful in the invention may fit the description of more than one of the groups described herein.

A first group of catalysts, then, are commonly referred to as First Generation Grubbs-type catalysts, and have the structure of formula (II). For the first group of catalysts, M and m are as described above, and n, X¹, X², L¹, L², L³, R¹, and R² are described as follows.

For the first group of catalysts, n is 0, and L¹ and L² are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, and thioether. Exemplary ligands are trisubstituted phosphines.

X¹ and X² are anionic ligands, and may be the same or different, or are linked together to form a cyclic group, typically although not necessarily a five- to eight-membered ring. In preferred embodiments, X¹ and X² are each independently hydrogen, halide, or one of the following groups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylsulfonato, C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₄ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, or C₅-C₂₄ arylsulfinyl. Optionally, X¹ and X² may be substituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄ aryl, and halide, which may, in turn, with the exception of halide, be further substituted with one or more groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl. In more preferred embodiments, X¹ and X² are halide, benzoate, C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl, phenoxy, C₁-C₆ alkoxy, C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆ alkylsulfonyl. In even more preferred embodiments, X¹ and X² are each halide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO, PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. In the most preferred embodiments, X¹ and X² are each chloride.

R¹ and R² are independently selected from hydrogen, hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl (e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and substituted heteroatom-containing hydrocarbyl (e.g., substituted heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functional groups. R¹ and R² may also be linked to form a cyclic group, which may be aliphatic or aromatic, and may contain substituents and/or heteroatoms. Generally, such a cyclic group will contain 4 to 12, preferably 5, 6, 7, or 8 ring atoms.

In preferred catalysts, R¹ is hydrogen and R² is selected from C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₄ aryl, more preferably C₁-C₆ alkyl, C₂-C₆ alkenyl, and C₅-C₁₄ aryl. Still more preferably, R² is phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substituted with one or more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, phenyl, and a functional group Fn as defined earlier herein. Most preferably, R² is phenyl or vinyl substituted with one or more moieties selected from methyl, ethyl, chloro, bromo, iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. Optimally, R² is phenyl or —C═C(CH₃)₂.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³, R¹, and R² can be taken together to form a cyclic group, as disclosed, for example, in U.S. Pat. No. 5,312,940 to Grubbs et al. When any of X¹, X², L¹, L², L³, R¹, and R² are linked to form cyclic groups, those cyclic groups may contain 4 to 12, preferably 4, 5, 6, 7 or 8 atoms, or may comprise two or three of such rings, which may be either fused or linked. The cyclic groups may be aliphatic or aromatic, and may be heteroatom-containing and/or substituted. The cyclic group may, in some cases, form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

A second group of catalysts, commonly referred to as Second Generation Grubbs-type catalysts, have the structure of formula (II), wherein L¹ is a carbene ligand having the structure of formula (III)

such that the complex may have the structure of formula (IV)

wherein M, m, n, X¹, X², L², L³, R¹, and R² are as defined for the first group of catalysts, and the remaining substituents are as follows.

X and Y are heteroatoms typically selected from N, O, S, and P. Since O and S are divalent, p is necessarily zero when X is O or S, and q is necessarily zero when Y is O or S. However, when X is N or P, then p is 1, and when Y is N or P, then q is 1. In a preferred embodiment, both X and Y are N.

Q¹, Q², Q³, and Q⁴ are linkers, e.g., hydrocarbylene (including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene, such as substituted and/or heteroatom-containing alkylene) or —(CO)—, and w, x, y, and z are independently zero or 1, meaning that each linker is optional. Preferably, w, x, y, and z are all zero. Further, two or more substituents on adjacent atoms within Q¹, Q², Q³, and Q⁴ may be linked to form an additional cyclic group.

R³, R^(3A), R⁴, and R^(4A) are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl.

In addition, any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) can be taken together to form a cyclic group, and any one or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) may be attached to a support.

Preferably, R^(3A) and R^(4A) are linked to form a cyclic group so that the carbene ligand has the structure of formula (V)

wherein R³ and R⁴ are defined above, with preferably at least one of R³ and R⁴, and more preferably both R³ and R⁴, being alicyclic or aromatic of one to about five rings, and optionally containing one or more heteroatoms and/or substituents. Q is a linker, typically a hydrocarbylene linker, including substituted hydrocarbylene, heteroatom-containing hydrocarbylene, and substituted heteroatom-containing hydrocarbylene linkers, wherein two or more substituents on adjacent atoms within Q may also be linked to form an additional cyclic structure, which may be similarly substituted to provide a fused polycyclic structure of two to about five cyclic groups. Q is often, although again not necessarily, a two-atom linkage or a three-atom linkage.

Examples of N-heterocyclic carbene ligands suitable as L¹ thus include, but are not limited to, the following:

When M is ruthenium, then, the preferred complexes have the structure of formula (VI)

In a more preferred embodiment, Q is a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, preferably —CR¹¹R¹²—CR¹³R¹⁴—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups. Examples of functional groups here include carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄ arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionally substituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹², R¹³, and R¹⁴ are preferably independently selected from hydrogen, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, phenyl, and substituted phenyl. Alternatively, any two of R¹, R², R³, and R¹⁴ may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring structure, e.g., a C₄-C₁₂ alicyclic group or a C₅ or C₆ aryl group, which may itself be substituted, e.g., with linked or fused alicyclic or aromatic groups, or with other substituents.

When R³ and R⁴ are aromatic, they are typically although not necessarily composed of one or two aromatic rings, which may or may not be substituted, e.g., R³ and R⁴ may be phenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like. In one preferred embodiment, R³ and R⁴ are the same and are each unsubstituted phenyl or phenyl substituted with up to three substituents selected from C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Preferably, any substituents present are hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ are mesityl.

In a third group of catalysts having the structure of formula (II), M, m, n, X¹, X², R¹, and R² are as defined for the first group of catalysts, L¹ is a strongly coordinating neutral electron donor ligand such as any of those described for the first and second group of catalysts, and L² and L³ are weakly coordinating neutral electron donor ligands in the form of optionally substituted heterocyclic groups. Again, n is zero or 1, such that L³ may or may not be present. Generally, in the third group of catalysts, L² and L³ are optionally substituted five- or six-membered monocyclic groups containing 1 to 4, preferably 1 to 3, most preferably 1 to 2 heteroatoms, or are optionally substituted bicyclic or polycyclic structures composed of 2 to 5 such five- or six-membered monocyclic groups. If the heterocyclic group is substituted, it should not be substituted on a coordinating heteroatom, and any one cyclic moiety within a heterocyclic group will generally not be substituted with more than 3 substituents.

For the third group of catalysts, examples of L² and L³ include, without limitation, heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³ include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine, pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole, 2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole, 1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine, indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline, cinnoline, quinazoline, naphthyridine, piperidine, piperazine, pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine, purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.

Examples of sulfur-containing heterocycles appropriate for L² and L³ include thiophene, 1,2-dithiole, 1,3-dithiole, thiepin, benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene, 2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³ include 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin, oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene, chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene, tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

Examples of mixed heterocycles appropriate for L² and L³ include isoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole, 1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole, 1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole, 1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine, 1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine, pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, and morpholine.

Preferred L² and L³ ligands are aromatic nitrogen-containing and oxygen-containing heterocycles, and particularly preferred L² and L³ ligands are monocyclic N-heteroaryl ligands that are optionally substituted with 1 to 3, preferably 1 or 2, substituents. Specific examples of particularly preferred L² and L³ ligands are pyridine and substituted pyridines, such as 3-bromopyridine, 4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine, 2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine, 3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine, 4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine, 3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine, 3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine, 2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine, 4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine, 3,5-dichloro-4-phenylpyridine, and the like.

In general, any substituents present on L² and/or L³ are selected from halo, C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ alkaryl, substituted C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substituted C₆-C₂₄ heteroalkaryl, C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄ heteroaralkyl, substituted C₆-C₂₄ heteroaralkyl, and functional groups, with suitable functional groups including, without limitation, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl, C₂-C₂₀ alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄ aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄ arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀ alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl, di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄ aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl, thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄ aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido, formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino, di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substituted amino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido, imino, C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. In addition, two adjacent substituents may be taken together to form a ring, generally a five- or six-membered alicyclic or aryl ring, optionally containing 1 to 3 heteroatoms and 1 to 3 substituents as above.

Preferred substituents on L and L³ include, without limitation, halo, C₁-C₁₂ alkyl, substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂ heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄ heteroaryl, substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substituted C₆-C₁₆ alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl, C₆-C₁₆ aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl, substituted C₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂ alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄ arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl, halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino, di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substituted amino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

Of the foregoing, the most preferred substituents are halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆ alkoxy, phenyl, substituted phenyl, formyl, N,N-diC₁-C₆ alkyl)amino, nitro, and nitrogen heterocycles as described above (including, for example, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine, pyridine, pyridazine, etc.).

L² and L³ may also be taken together to form a bidentate or multidentate ligand containing two or more, generally two, coordinating heteroatoms such as N, O, S, or P, with preferred such ligands being diimine ligands of the Brookhart type. One representative bidentate ligand has the structure of formula (VII)

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ hydrocarbyl (e.g., C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄ aralkyl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄ aralkyl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl, C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, or heteroatom-containing C₆-C₂₄ alkaryl), or substituted heteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl, C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, or heteroatom-containing C₆-C₂₄ alkaryl), or (1) R¹⁵ and R¹⁶, (2) R¹⁷ and R¹⁸, (3) R¹⁶ and R¹⁷, or (4) both R¹⁵ and R¹⁶, and R¹⁷ and R¹⁸, may be taken together to form a ring, i.e., an N-heterocycle. Preferred cyclic groups in such a case are five- and six-membered rings, typically aromatic rings.

In a fourth group of catalysts that have the structure of formula (I), two of the substituents are taken together to form a bidentate ligand or a tridentate ligand. Examples of bidentate ligands include, but are not limited to, bisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Specific examples include —P(Ph)₂CH₂CH₂P(Ph)₂-, —As(Ph)₂CH₂CH₂As(Ph₂)—, —P(Ph)₂CH₂CH₂C(CF₃)₂O—, binaphtholate dianions, pinacolate dianions, —P(CH₃)₂(CH₂)₂P(CH₃)₂—, and —OC(CH₃)₂(CH₃)₂CO—. Preferred bidentate ligands are —P(Ph)₂ CH₂CH₂P(Ph)₂- and —P(CH₃)₂(CH₂)₂P(CH₃)₂—. Tridentate ligands include, but are not limited to, (CH₃)₂ NCH₂CH₂P(Ph)CH₂CH₂N(CH₃)₂. Other preferred tridentate ligands are those in which any three of X¹, X², L¹, L², L³, R¹, and R² (e.g., X¹, L¹, and L²) are taken together to be cyclopentadienyl, indenyl, or fluorenyl, each optionally substituted with C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀ alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, each of which may be further substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenyl group optionally substituted with halide, C₁-C₆ alkyl, or C₁-C₆ alkoxy. More preferably, in compounds of this type, X, L¹, and L² are taken together to be cyclopentadienyl or indenyl, each optionally substituted with vinyl, C₁-C₁₀ alkyl, C₅-C₂₀ aryl, C₁-C₁₀ carboxylate, C₂-C₁₀ alkoxycarbonyl, C₁-C₁₀ alkoxy, or C₅-C₂₀ aryloxy, each optionally substituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenyl group optionally substituted with halide, C₁-C₆ alkyl or C₁-C₆ alkoxy. Most preferably, X, L¹ and L² may be taken together to be cyclopentadienyl, optionally substituted with vinyl, hydrogen, methyl, or phenyl. Tetradentate ligands include, but are not limited to O₂C(CH₂)₂P(Ph)(CH₂)₂P(Ph)(CH₂)₂CO₂, phthalocyanines, and porphyrins.

Complexes wherein L² and R² are linked are examples of the fourth group of catalysts, and are commonly called “Grubbs-Hoveyda” catalysts. Examples of Grubbs-Hoveyda-type catalysts include the following:

wherein L¹, X¹, X², and M are as described for any of the other groups of catalysts.

In addition to the catalysts that have the structure of formula (II), as described above, other transition metal carbene complexes include, but are not limited to:

neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 16, are penta-coordinated, and are of the general formula (VIII);

neutral ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 18, are hexa-coordinated, and are of the general formula (IX);

cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14, are tetra-coordinated, and are of the general formula (X); and

cationic ruthenium or osmium metal carbene complexes containing metal centers that are formally in the +2 oxidation state, have an electron count of 14, are penta-coordinated, and are of the general formula (XI)

wherein: X¹, X², L¹, L², n, L¹, R¹, and R² are as defined for any of the previously defined four groups of catalysts; r and s are independently zero or 1; t is an integer in the range of zero to 5; Y is any non-coordinating anion (e.g., a halide ion, BF₄—, etc.); Z¹ and Z² are independently selected from —O—, —S—, —NR²—, —PR²—, —P(═O)R²—, —P(OR²)—, —P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—, —OC(═O)O—, —S(═O)—, and —S(═O)₂—; Z³ is any cationic moiety such as —P(R²)₃ ⁺ or —N(R²)₃ ⁺; and any two or more of X¹, X², L¹, L², L³, n, Z¹, Z², Z³, R¹, and R² may be taken together to form a cyclic group, e.g., a multidentate ligand, and wherein any one or more of X, X², L¹, L², n, L³, Z¹, Z², Z³, R¹, and R² may be attached to a support.

As is understood in the field of catalysis, suitable solid supports for any of the catalysts described herein may be of synthetic, semi-synthetic, or naturally occurring materials, which may be organic or inorganic, e.g., polymeric, ceramic, or metallic. Attachment to the support will generally, although not necessarily, be covalent, and the covalent linkage may be direct or indirect, if indirect, typically through a functional group on a support surface.

Non-limiting examples of catalysts that may be used in the reactions disclosed herein include the following, some of which for convenience are identified throughout this disclosure by reference to their molecular weight:

In the foregoing molecular structures and formulae, Ph represents phenyl, Cy represents cyclohexyl, Me represents methyl, nBu represents n-butyl, i-Pr represents isopropyl, py represents pyridine (coordinated through the N atom), and Mes represents mesityl (i.e., 2,4,6-trimethylphenyl).

Further examples of catalysts useful in the reactions disclosed herein include the following: ruthenium (II) dichloro(3-methyl-1,2-butenylidene) bis(tricyclopentylphosphine) (C716); ruthenium (II) dichloro(3-methyl-1,2-butenylidene) bis(tricyclohexylphosphine) (C801); ruthenium (II) dichloro(phenylmethylene) bis(tricyclohexylphosphine) (C823); ruthenium (II) [1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene) dichloro (phenylmethylene) (triphenylphosphine) (C830), and ruthenium (II) dichloro(vinyl phenylmethylene) bis(tricyclohexylphosphine) (C835); ruthenium (II) dichloro (tricyclohexylphosphine) (o-isopropoxyphenylmethylene) (C601), and ruthenium (II) (1,3-bis-(2,4,6,-trimethylphenyl)-2-imidazolidinylidene) dichloro(phenylmethylene) (bis 3-bromopyridine (C884)).

Still further catalysts useful in the ring-opening cross-methathesis (ROCM) reactions disclosed herein include the following, identified as structures 60-68:

The transition metal complexes used as catalysts herein can be prepared by several different methods, such as those described by Schwab et al. (1996) J. Am. Chem. Soc. 118: 100-110, Scholl et al. (1999) Org. Lett. 6:953-956, Sanford et al. (2001) J. Am. Chem. Soc. 123:749-750, U.S. Pat. No. 5,312,940 and U.S. Pat. No. 5,342,909. Also see U.S. Patent Publication No. 2003/0055262 to Grubbs et al. filed Apr. 16, 2002 for “Group 8 Transition Metal Carbene Complexes as Enantioselective Olefin Metathesis Catalysts”, International Patent Publication No. WO 02/079208 application Ser. No. 10/115,581 to Grubbs, Morgan, Benitez, and Louie, filed Apr. 2, 2002, for “One-Pot Synthesis of Group 8 Transition Metal Carbene Complexes Useful as Olefin Metathesis Catalysts,” commonly assigned herewith to the California Institute of Technology. Preferred synthetic methods are described in International Patent Publication No. WO 03/11455A1 to Grubbs et al. for “Hexacoordinated Ruthenium or Osmium Metal Carbene Metathesis Catalysts,” published Feb. 13, 2003.

The components of the reactions disclosed herein may be combined in any order, and it will be appreciated that the order of combining the reactants may be adjusted as needed. For example, the olefinic substrate may be added to the cross-metathesis partner, followed by addition of the catalyst. Alternatively, the olefinic substrate and cross-metathesis partner may be added to the catalyst. When one of the reactants is a gas, it may be necessary to add the catalyst to the liquid or solid reactant before introducing the gaseous reactant.

The catalyst may be added to the reaction either as a solid, dissolved in one of the reactants, or dissolved in a solvent.

The reactions disclosed herein may be carried out in a solvent, and any solvent that is inert towards cross-metathesis may be employed. Generally, solvents that may be used in the cross-metathesis reactions include organic, protic, or aqueous solvents, such as aromatic hydrocarbons, chlorinated hydrocarbons, ethers, aliphatic hydrocarbons, alcohols, water, or mixtures thereof. Example solvents include benzene, toluene, p-xylene, methylene chloride, 1,2-dichloroethane, dichlorobenzene, chlorobenzene, tetrahydrofuran, diethylether, pentane, methanol, ethanol, water, or mixtures thereof. In a preferred embodiment, the reactions disclosed herein are carried out neat, i.e., without the use of a solvent.

It will be appreciated that the temperature at which a cross-metathesis reaction according to methods disclosed herein is conducted can be adjusted as needed, and may be at least about −78° C., −40° C., −10° C., 0° C., 10° C., 20° C., 25° C., 35° C., 50° C., 70° C., 100° C., or 150° C., or the temperature may be in a range that has any of these values as the upper or lower bounds. In a preferred embodiment, the reactions are carried out at a temperature of at least about 35° C., and in another preferred embodiment, the reactions are carried out at a temperature of at least about 50° C.

It will further be appreciated that the molar ratio of the reactants will be dependent upon the identities of the reactants and the desired products. Although the cyclic olefin and the olefinic substrate may be used in equal molar amounts, in general, an excess of cyclic olefin with respect to the olefinic substrate will be present. For example, the molar ratio of the cyclic olefin (as the sum of all compounds when the cyclic olefin comprises a plurality of cyclic compounds) to the olefinic substrate may be up to 2:1, 5:1, 10:1, 25:1, 50:1, 100:1, 250:1, 500:1, 1000:1, 5000:1, 10,000:1, 50,000:1, or 100,000:1, or within a range that has any of these values as the upper or lower bounds.

When the cyclic olefin comprises a cyclic olefinic hydrocarbon and a cyclic alkenol, the molar ratio of the two compounds will vary depending on the desired products. For example, the molar ratio of the cyclic olefinic hydrocarbon to the cyclic alkenol may be 100:1, 50:1, 25:1, 10:1, 5:1, 2:1, 1:1, 1:2, 1:5, 1:10, 1:25, 1:50, or 1:100, or within a range that has any of these values as the upper or lower bounds.

II. SECOND EMBODIMENT Further Reactions

In a second embodiment, the invention provides a method for manufacturing a wax. The method involves ring-opening, ring insertion metathesis of at least one olefinic substrate and at least one cyclic olefin as the cross metathesis partner. As with the first embodiment, the olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The reaction is carried out catalytically, generally in the presence of a ruthenium alkylidene metathesis catalyst, by contacting the at least one olefinic substrate with the cross metathesis partner, i.e., the at least one cyclic olefin, in the presence of the metathesis catalyst under reaction conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate to provide an olefinic product. This embodiment further comprises partially or completely hydrogenating the olefinic product. The disclosure, supra, with respect to the components and methods of the first embodiment also applies to the second embodiment.

Methods suitable for carrying out the partial or complete hydrogenation of the olefinic product are known in the art, and any appropriate hydrogenation method may be employed. Typically, such methods involve placing the olefinic product in a suitable container, introducing a hydrogenation catalyst, if necessary, and introducing a hydrogen source. Suitable methods for hydrogenation may be found, for example, in Smith et al. March's Advanced Organic Chemistry, 5th Edition (Wiley: New York, 2001).

The hydrogenation of the olefinic product of the reaction may be carried out with or without isolation of the olefinic products from the ring insertion cross metathesis reaction. It will be appreciated that the hydrogenation reaction will, in some instances, be affected by the purity of the reaction mixture and the presence of impurities from the ring insertion cross metathesis reaction. In such cases, the yield of the hydrogenated olefinic products can be maximized by isolating and purifying the olefinic products before hydrogenation is performed.

Any catalyst suitable for hydrogenating the olefinic products may be employed, and appropriate catalysts may also be found, for example, in Smith et al. March's Advanced Organic Chemistry, 5th Edition (Wiley: New York, 2001). In one example, the ruthenium alkylidene metathesis catalysts that is used for the ring insertion cross metathesis reaction may also be employed as the hydrogenation catalyst. In this embodiment, it is not necessary to add a further hydrogenation catalyst to the reaction mixture in order to perform the hydrogenation.

III. THIRD EMBODIMENT Process with the Grubbs-Hoveyda Catalyst

In a third embodiment, the invention provides an olefin cross-metathesis method in which the method involves ring-opening, ring insertion metathesis of at least one olefinic substrate and at least one cyclic olefin as the cross metathesis partner. The reaction is carried out catalytically, generally in the presence of a ruthenium alkylidene metathesis catalyst. In this embodiment, the reaction is carried out by contacting the at least one olefinic substrate with the cross metathesis partner, i.e., the at least one cyclic olefin, in the presence of the metathesis catalyst under reaction conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate. Furthermore, in this embodiment, the catalyst is a Grubbs-Hoveyda complex, as described in detail for the first embodiment, supra.

IV. FOURTH EMBODIMENT Reaction System

In a fourth embodiment, the invention provides a reaction system. As an example, a reaction system is provided for carrying out a catalytic ring-opening cross-metathesis reaction comprising at least one olefinic substrate, at least one cyclic olefin, and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The reaction system may further comprise a solvent.

In a second example of this embodiment, the reaction mixture comprises at least one olefinic substrate, an unsubstituted cyclic olefin, a cyclic alkenol, and a ruthenium alkylidene metathesis catalyst.

In another example, a reaction system is provided for manufacturing a wax. The reaction system comprises at least one olefinic substrate, at least one cyclic olefin, and a ruthenium alkylidene olefin metathesis catalyst. The at least one olefinic substrate is selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol.

Detailed descriptions of each of these reaction components can be found in the disclosure of the first embodiment, supra.

V. FIFTH EMBODIMENT Products

In a fifth embodiment, the invention provides compounds and compositions. For example, the invention provides compounds that are prepared using any of the reactions and/or reaction systems disclosed herein. Such compounds may be monomers, dimmers, trimers, oligomers, higher order species, or mixtures thereof. Such compounds may be chain-extended olefinic substrates such as glycerides. Examples of chain-extended glycerides include chain-extended monoglycerides, chain-extended diglycerides, chain-extended triglycerides, higher order chain-extended glycerides, and combinations thereof.

VI. SIXTH EMBODIMENT Kit of Parts

In a fifth embodiment, the invention provides a kit of parts. As an example, a kit of parts is provided for carrying out a catalytic ring-opening cross metathesis reaction. The kit of parts comprises at least one olefinic substrate and a ruthenium alkylidene olefin metathesis catalyst. The catalyst is present in an amount that is less than 1000 ppm relative to the olefinic substrate, and the at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The kit of parts further comprises: (a) at least one cyclic olefin; or (b) instructions for adding a cyclic olefin to the at least one olefinic substrate. The at least one olefinic substrate, the ruthenium alkylidene olefin metathesis catalyst, and the at least one cyclic olefin (when present) may be combined in a mixture or may be contained separately.

In a preferred embodiment of the kit of parts for carrying out a catalytic ring-opening cross metathesis reaction, the kit comprises at least one cyclic olefin. The at least one olefinic substrate is combined in a mixture with the at least one olefinic substrate, and this mixture is contained separately from the ruthenium alkylidene olefin metathesis catalyst.

In another example, a kit of parts is provided for manufacturing a wax. The kit of parts comprises at least one olefinic substrate and a ruthenium alkylidene olefin metathesis catalyst. The catalyst is present in an amount that is less than 1000 ppm relative to the olefinic substrate, and the at least one olefinic substrate is selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol. The kit of parts further comprises: (a) at least one cyclic olefin; or (b) instructions for adding a cyclic olefin to the at least one olefinic substrate. The kit of parts further comprises instructions for hydrogenating metathesis products, and the kit may further comprises materials useful for hydrogenating metathesis products.

In a preferred embodiment of the kit of parts for manufacturing a wax, the kit comprises at least one cyclic olefin. The at least one olefinic substrate is combined in a mixture with the at least one olefinic substrate, and this mixture is contained separately from the ruthenium alkylidene olefin metathesis catalyst.

Detailed descriptions of each of these reaction components can be found in the disclosure of the first embodiment, supra.

Utility

The metathesis products from the methods disclosed herein are useful, for example, as binders in urethane foams, latex paints, printing inks and as high melting point waxes. As described hereinabove, the double bonds may be partially or completely hydrogenated to produce waxes of varying melting points.

It is to be understood that while the invention has been described in conjunction with specific embodiments thereof, that the description above as well as the examples that follow are intended to illustrate and not limit the scope of the invention. Other aspects, advantages, and modifications within the scope of the invention will be apparent to those skilled in the art to which the invention pertains.

EXPERIMENTAL

In the following examples, efforts have been made to ensure accuracy with respect to numbers used (e.g., amounts, temperature, etc.) but some experimental error and deviation should be accounted for. Unless indicated otherwise, temperature is in degrees C. and pressure is at or near atmospheric.

EXAMPLES

General Metathesis Procedure for Production and Analysis of Metathesized Oil Polyol and Chain-Extended Samples. To a clean and dry 2-L round-bottomed flask is added approximately 500 g of seed oil (e.g., refined bleached deodorized soybean oil (RBDSBO), Castor Oil, volatile lights removed metathesized soybean oil (RMSBO), soybean oil fatty acid methyl esters (Soy FAME), caster oil fatty acid methyl estsers (Castor FAME), etc.) containing a PTFE lined stir bar. To the oil is added one or more reagents (e.g., cyclooctene, 5-hydroxymethyl-2-norbornene, etc.), in mole ratio ranging from 0.1 mol % to 200 mol %. The mixture is degassed with Argon for one hour with stirring. After degassing, an appropriate mass of metathesis catalyst such as C827 (1) (i.e., [1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene]dichloro[3-methyl-2-buteneylidene]-tricyclohexylphosphine) ruthenium) is added as a solid to the reaction mixture at room temperature, at which point the vessel is blanketed with Argon, sealed, and placed in a 70° C. oil bath. When the temperature of the bath reaches 70° C. again, the time is recorded and the reaction is allowed to stir for two hours. The catalyst may be removed or the reaction mixture can be used without further purification. After two hours, an aliquot is taken from the reaction and added to about 1 mL of 1% NaOMe/MeOH solution in a vial, which is placed in a heating block at 70° C. for 30 min in order to transesterify the triglyceride products into methyl esters. After 30 min, the solution is allowed to cool. The cooled solution is hydrolyzed, and then the organics extracted using a relatively non-polar solvent (e.g., hexanes, ether, etc.). The organic layer is analyzed by GC; unless otherwise noted, conversion is calculated and reported based on the disappearance of the starting material. It is noted whether all or some of the reaction solidified, and, in some cases, a viscosity measurement is taken.

Catalyst Removal Procedure: A 1.0 M solution of tris(hydroxymethyl)phosphine (THMP) in isopropanol (IPA) (25 mol equiv of THMP per mole of metathesis catalyst) was added to the metathesized oil and the mixture was heated at 70° C. for 6 hours (under argon) (R. L. Pederson; I. M. Fellows; T. A. Ung; H. Ishihara; S. P Hajela Adv. Syn. Cat. 2002, 344, 728). Hexanes was added if needed to form a second phase when the mixture was washed 3 times with water. The organic phase was dried with anhydrous Na₂SO₄, filtered and analyzed by GC analysis.

Alternative Catalyst Removal Procedure: A 1.0 M solution of tris(hydroxymethyl)phosphine (THMP) in IPA (25 mol equiv of THMP per mole of metathesis catalyst) was added to the metathesized oil and the mixture was heated at 70° C. for 6 hours (under argon) (R. L. Pederson; I. M. Fellows; T. A. Ung; H. Ishihara; S. P Hajela Adv. Syn. Cat. 2002, 344, 728). IPA was then removed via rotary evaporator (part of volatile terminal olefins were also removed), 5 wt % of bleaching clay (Pure Flow B80 CG) to product was added to the crude reaction mixture and stirred overnight under argon at 70° C. The crude product mixture containing the clay was subsequently filtered through a packed bed of sand (10 g), celite (5 g), bleaching clay (12.5 g), and sand (10 g). The filtered oil was analyzed by GC analysis.

General Procedure for the Transesterification of Metathesized Seed oils: To a glass 3-necked round bottom flask with a magnetic stirrer, condenser, temperature probe, and a gas adapter was charged with crude metathesized SBO product (˜1 L) and 1% w/w NaOMe in MeOH (˜3 L). The resulting light yellow heterogeneous mixture was stirred at 60° C. for 1 hr. Towards the end of the hour, the mixture turned a homogeneous orange color. Esterified products were transferred into the separatory funnel and extracted with 2.0 L D₁-H₂O. The aqueous layer was then extracted with 2×2.0 L Et₂O. The combined organic extracts were dried over 300 g. of anhydrous Na₂SO₄ for 20 hours. The solution of esterified products was filtered and the filtrate was stripped of solvent via rotary evaporator.

Viscosity methods: All readings were taken at 30° C. using a Brookfield Digital Viscometer Model DV-II and S62 spindle. RPM values were dependent on individual viscosity of the material.

GC Analysis Conditions and methods: The products were analyzed using an Agilent 6890 gas chromatography (GC) instrument with a flame ionization detector (FID). The following conditions and equipment were used: Column: Rtx-5, 30 m × 0.25 mm (ID) × 0.25 μm film thickness. Manufacturer: Restek GC and column Injector temperature: 250° C. conditions: Detector temperature: 280° C. Oven temperature: Starting temperature: 100° C., hold time: 1 minute. Ramp rate 10° C./min to 250° C., hold time: 12 minutes. Carrier gas: Helium Mean gas velocity: 31.3 ± 3.5% cm/sec (calculated) Split ratio: ˜50:1 The products were characterized by comparing peaks with known standards, in conjunction with supporting data from mass spectrum analysis (GCMS-Agilent 5973N). GCMS analysis was accomplished with a second Rtx-5, 30 m×0.25 mm (ID)×0.25 μm film thickness GC column, using the same method as above.

Materials and methods: Seed oils were obtained from Cargill. In the Examples that follow, all reactions were carried out using the specified catalyst loading as moles of catalyst to moles of seed oils. Catalysts are referenced using their molecular weights, as described hereinabove. In the Examples, the abbreviation RMSBO refers to Removed-Lights Metathesized Soy Bean Oil, which is self-metathesized RBSBO in which the light oils and olefins have been removed by flash distillation. Self-metathesis of seed oils is described in WO 2006/076364. Reference is also made to various cyclic olefins using the following abbreviations:

Example 1

Various compounds were analyzed using the GCMS methods described above. Data are provided in table 1. TABLE 1 Common Products from the Cross Metathesis of Seed Oils. Compound Ret Time (min) Compound Abbreviation 1.300 E-2-Octene 2C₈ 1.596 3-Nonene 3C₉ 2.039 1-Decene 1C₁₀ 2.907 E-2-Undecene E-2C₁₁ 3.001 Z-2-Undecene Z-2C₁₁ 3.836 3-Dodecenes 3C₁₂ 5.298 Methyl 9-Decenoate 9C₁₀O₂Me 7.419 Pentadecadienes nC₁₅ 7.816 Methyl E-9-Dodecenoate E-9C₁₂O₂Me 7.894 Methyl Z-9-Dodecenoate Z-9C₁₂O₂Me 10.939 9-Octadecene 9C₁₈ 11.290 Methyl 9-12 tetradecadienoate 9,12C₁₄O₂Me 12.523 Methyl palmitate C₁₆O₂Me 14.306 Methyl linoleates 9,12C₁₈O₂Me 14.363 Methyl oleates 9C₁₈O₂Me 14.537 Methyl stearate C₁₈O₂Me 17.138 Methyl 9,21-Henicosadienaote 9,12C₁₈O₂Me 17.586 1,18 Dimethyl ester of 9-Ocadecene 9,12C₁₈O₂Me 22.236 Methyl 9,12,15-docosatrienoate 9,12,15C₂₁O₂Me

Example 2

A model study was undertaken to prove that ROCM reactions produced the desired higher molecular weight products. This study examined reaction of simple acyclic olefins with cyclooctene to determine and characterize the ROCM products formed.

In a ROCM reaction, a cyclic alkene undergoes the ring-opening metathesis reaction to produce the mixture of ring-opened products. Once opened, it will cross metathesize with an acyclic alkene such as SBO or SBO FAME to yield a new high molecular weight product. Hence the ROCM product should be a mixture of cyclic alkene inserted-products. To understand the ROCM product distributions, several ROCM reactions have been studied under different ratios of cyclic alkene to acyclic alkene.

GC and GC-MS Results of ROCM Products:

Conversion in each reaction was determined by measuring the disappearance of the starting internal alkene when compared to dodecane as an internal standard. The GC and GC-MS analyses were determined and ROCM products were characterized up to n=3 cyclic olefin inserted products. When n was >3, these products were above our detection limit of our instruments. The ratio of higher than 3-ring inserted product was found to increase with higher loading of cycloalkene.

GC and GC-MS Analysis of ROCM Products:

Well defined olefins were run under ROCM conditions with cyclic olefins to yield higher molecular weight products. GC and GC-MS analysis of these products identified up to 3 cyclic ring inserted compounds. The ring inserted products were characterized by GC and their molecular weights were determined by GC-MS analysis. The detection limit of our GC and GC-MS was n=3; when n>3 higher molecular weight products did not elute as sharp interpretable peaks. The n>3 value represents high molecular products that were not identified by GC or GC-MS, this value was calculated by 100% minus percent unreacted starting minus n=1, n=2 and n=3 percentages. The data below demonstrates the product distributions for the ratios of starting materials indicated.

I. GC Results of ROCM of 9-Octadecene (9C18) and Cyclooctene and Cyclododecene.

% insertion product m % SM^(a) n = 1 n = 2 n = 3 n>3 0.5 42 14 2 <1 42 1 49 19 8 4 20 2 31 20 9 <1 40 3 23 17 11 1 48 5 15 11 7 1 66 10 14 6 4 <1 77 ^(a)% SM represents the amount of unreacted starting acyclic olefin present at the end of the reaction.

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 47 13 7 <1 33

FIG. 1 depicts a typical GC-MS chromatogram of ROCM (n=1) products. The peaks at 20.10 min to 20.40 min are cis and trans-isomers of the n=1 ROCM product. The molecular weights of these peaks were determined to be 362, which corresponds to the product.

FIG. 2 depicts the MALD-TOF study of 9C18 and COE ROCM reactions. The reaction was run in a potassium salt matrix which explains why the molecular weights are 56 units higher than expected. The data clearly shows that each 110 repeat unit (when n=1 to 7) corresponds to another insertion of COE. With this technique, repeat units of up to n=7 COE inserted units have been identified. The GC-MS and MALDI-TOF data clearly demonstrated that the COE units are being inserted into the 9-octadecene to produce the desired ROCM high molecular weight products.

II. GC Results of ROCM of 1,18-Dimethyl esters of 9-Octadecene (9C18-diester) with Cyclooctene, Cyclododecene or Norbornene Ethylene Glycol Ester (NBE).

% insertion product m % SM n = 1 n = 2 n = 3 n>3 0.5 65 16 2 <1 18 1 68 15 4 <1 13 2 32 16 5 <1 48 3 25 31 7 <1 37 5 17 10 3 <1 70 10 10 5 1 <1 84

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 42 6 13 <1 38

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 70 3 <3 <3 27

III. GC Results of ROCM of Methyl Oleate (MO) with Cyclooctene, Cyclododecene or Norbornene Ethylene Glycol Ester (NBE).

% insertion product m % SM n = 1(A,B,C) n = 2(A,B,C) n = 3 n>3 0.5 64 15(5,8,2) 2(1,1,0) 1 18 1 46 14(4,7,3) 6(1,3,2) 2 32 2 31 18(5,9,4) 9(3,5,1) 1 40 3 26 18(5,9,4) 9(3,5,1) 2 46 5 22  9(2,5,2) 3(1,2,1) 1 65 10 17  7(2,4,1) 2(1,1,0) <1 74

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 46 14 4 <1 37

% insertion product m % SM n = 1 n = 2 n = 3 n>3 1 46 4 <1 <1 50

IV. GC Results of ROCM of Castor Oil Fatty Acid Methyl Ester (Castor Fame) with Cyclooctene

% insertion product m % SM n = 1(A,B,C) n = 2(A,B,C) n = 3 n>3 0.5 58 14(4,7,3) 2(1,1,0) <1 26 1 52 19(4,10,5) 7(1,4,2) <1 22 2 31 16(4,8,4) 6(2,4,0) <1 47 3 25 14(4,7,3) 7(2,4,1) <1 54 5 16 10(3,5,2) 5(1,3,1) <1 70 10 13  7(2,4,1) 3(1,1,1) 1 77

These results demonstrated that the cyclic olefins are inserted into the seed oils, up to our level of detection by GC and GC-MS. Moreover, these results indicated that the reactions using higher ratios of cyclic olefins to acyclic alkene produced higher molecular weight products as determined by the lower ratio of unreacted starting materials, n=1, n=2 and n=3 detectable products, thereby it is possible to control the molecular weight of product. To further prove ROCM products, MALDI-TOF analysis was done on sample JP.125.193B. This data clearly shows insertion of the cyclooctene up to n=7 increasing repeat units.

Example 3

Using the General Metathesis procedure described above, various FAMEs were reacted with various cyclic olefins using the ruthenium alkylidene metathesis catalyst C827. The results are given in Table 2. TABLE 2 Ring Opening Cross Metathesis Products Cyclic FAME Olefin C827 Conv.¹ Cyclic Reaction # FAME Cyclic Olefin mol % (ppm) (Y/N) Conv.¹ (Y/N) JP.125.085 MO No 200 Y NA JP.125.051M ML No 200 Y NA JP.125.184G None NBM None NA NA JP.125.184H None NBE None NA NA JP.125.084K None Cydecanol None NA NA JP.125.084E None NBM 200 Solid, no GC JP.125.084F None NBE 200 Solid, no GC CWL81-143 None Cydecanol 200 N JP.125.084A MO NBM 50 None NA NA JP.125.084B MO NBE 50 None NA NA JP.125.084I MO Cydecanol 50 None NA NA JP.125.084C ML NBM 50 None NA NA JP.125.084D ML NBE 50 None NA NA JP.125.084J ML Cydecanol 50 None NA NA JP.125.051A MO NBM 50 200 Y Y JP.125.051B MO NBM 20 200 Y Y JP.125.051C MO NBM 10 200 Y Y JP.125.051D MO NBE 50 200 Y Y JP.125.051E MO NBE 20 200 Y Y JP.125.051F MO NBE 10 200 Y Y CWL81- MO Cydecanol 50 200-100 Y N 143A JP.125.051G ML NBM 50 200 Y Y JP.125.051H ML NBM 20 200 Y Y JP.125.051I ML NBM 10 200 Y Y JP.125.051H ML NBE 50 200 Y Y JP.125.051K ML NBE 20 200 Y Y JP.125.051L ML NBE 10 200 Y Y JP.125.066 ML Cydecanol 50 200 Y N ¹Conv.: refers to whether metathesis occurred with each individual material; not a numerical value.

The data in Table 2 demonstrate that various FAMEs and cyclic olefins are good substrates for metathesis. However, cyclecanol was a poor substrate for metathesis under the standard reaction conditions (likely due to low ring strain) but did not negatively impact metathesis of other olefins with which it was mixed.

Example 4

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO and either NBM or NBE. The results are provided in Table 3. Conversion percent refers to the amount of new metathesis products formed as calculated by 100% minus the percent of unreacted starting materials. TABLE 3 Ring insertion cross metathesis of SBO with NBM or NBE Cyclic Seed Oil/ Cyclic olefin C827 Conv. Product Viscosity Reaction # Batch # Olefin mol % (ppm) (%) a Solid^(a) (cP)^(b) AV078-114C SBO/F5L19 — 0 50 68 N 189 JP.105.128 SBO/F5L19 NBM 5 50 67 JP.105.142 SBO/F5L19 NBM 20 50 54 198 CWL81-108 SBO/F5L19 NBE 5 50 69 192 CWL81-109A SBO/F5L19 NBE 5 100 70 132 CWL81-109B SBO/F5L19 NBE 10 50 69 186 CWL81-109C SBO/F5L19 NBE 10 100 69 240 CWL81-110A SBO/F5L19 NBE 20 50 67 230 CWL81-110B SBO/F5L19 NBE 20 100 69 276 JP.105.171 SBO/F5L19 NBE 35 100 67 Y JP.105.172 SBO/F5L19 NBE 50 100 68 Y 3780 JP.105.184 SBO/F5L19 NBE 100 100 62 Y JP.105.160 SBO/F5L19 NBE 200 400 70 Y ^(a)Metathesis product was a solid or precipitated. ^(b)Viscosities were measured at 30˜40 C. using S62 spindle with Brookfield DV-II+ viscometer

The data demonstrates that NBM and NBE are substrates for ROCM reactions. The metathesis of neat SBO will reach 68% conversion at equilibrium. ROCM products are shown by the increased viscosity reading of the ROCM products compared to neat SBO.

Example 5

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO/F5L19 as olefinic substrate and Cyclol as cyclic olefin. The results are provided in Table 4. TABLE 4 Ring opening cross metathesis of SBO and Cydol Cyclic Olefin Viscosity Reaction # mol % C827 (ppm) Conv. (%) (cP) AV078-114C 0 50 68 189 JP.105.122 5 50 65 173 JP.105.124 5 100 68 179 JP.105.123 10 50 64 JP.105.125 10 100 67 160 JP.105.126 20 50 63 179 JP.105.127 20 100 68 170 JP.105.173 35 100 63 JP.105.174 50 100 53 JP.105.161 100 200 68 JP.105.162 200 200 56 Cydol is a poor substrate for metathesis ROCM applications but it does not have an inhibitory effect on the metathesis catalyst.

Example 6

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO/F5L19 as olefinic substrate and with HNB, NBM and Cyclol as cyclic olefins. The results are provided in Table 5. TABLE 5 Ring insertion cross metathesis of SBO and HNB Cyclic Olefin C827 Conv. Reaction # Cyclic Olefin mol % (ppm) (%) CWL81-124A HNB/NBM 10/0.2 50 69 CWL81-124B HNB/NBM 10/1.0 50 69 CWL81-126A HNB/NBE 10/1.0 50 70 CWL81-126B HNB/NBE 20/1.0 50 70 CWL81-127A HNB/Cydol 10/1.0 50 69 CWL81-127B HNB/Cydol 20/1.0 50 68 HNB, NBE, NBM and Cydol do not have an inhibitory effect on the metathesis catalyst or the metathesis of SBO.

Example 7

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO as olefinic substrate and BNB, NBM, NBE and Cyclol as cyclic olefins. The results are provided in Table 6. TABLE 6 Ring insertion cross metathesis of SBO and BNB Cyclic Seed Oil/ Olefin C827 Conv. Reaction # Batch # Cyclic Olefin mol % (ppm) (%) JP.125.064 SBO/F6C13 BNB/NBM 100/20 200 67 JP.125.065 SBO/F6C13 BNB/NBM 200/20 300 66 JP.125.013 SBO/F5J26 BNB/NBE  50/10 100 69 JP.125.014 SBO/F5J26 BNB/NBE 100/10 100 66 JP.125.015 SBO/F5J26 BNB/NBE 100/20 200 68 JP.125.016 SBO/F5J26 BNB/NBE 200/20 300 67 JP.125.026 SBO/F5J26 BNB/Cydol  50/10 100 69 JP.125.027 SBO/F5J26 BNB/Cydol 100/10 100 68 JP.125.028 SBO/F5J26 BNB/Cydol 100/20 200 69 JP.125.029 SBO/F5J26 BNB/Cydol 200/20 300 68

BNB, NBM, NBE and Cyclol do not have an inhibitory effect on the metathesis catalyst.

Example 8

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO as olefinic substrate and COE, NBM, NBE and Cyclol as the cyclic olefins. The results are provided in Table 7. TABLE 7 Ring insertion cross metathesis of SBO and COE Cyclic Seed Oil/ Olefin C827 Conv. Viscosity Reaction # Batch # Cyclic Olefin mol % (ppm) (%) (cP) JP.105.155 SBO/F5L19 COE/NBM 10/1.0 50 64 JP.125.052 SBO/F6C13 COE/NBM 50/10  100 70 JP.125.054 SBO/F6C13 COE/NBM 100/20   200 71 JP.125.055 SBO/F6C13 COE/NBM 200/20   300 73 256 CWL81-129A SBO/F5L19 COE/NBE 10/1.0 50 70 CWL81-129B SBO/F5L19 COE/NBE 20/1.0 50 70 CWL81-136B SBO/F5L19 COE/NBE 50/1.0 100 72 179 JP.105.208 SBO/F5J26 COE/NBE 50/10  100 68 CWL81-136A SBO/F5L19 COE/NBE 100/10   100 71 JP.125.017 SBO/F5J26 COE/NBE 100/20   100 70 JP.125.018 SBO/F5J26 COE/NBE 200/20   200 76 468 CWL81-128A SBO/F5L19 COE/Cydol 10/1.0 50 69 CWL81-128B SBO/F5L19 COE/Cydol 20/1.0 50 69 CWL81-135B SBO/F5L19 COE/Cydol 50/1.0 100 72 CWL81-137B SBO/F5L19 COE/Cydol 50/10  100 71 CWL81-135A SBO/F5L19 COE/Cydol 100/10   100 71 CWL81-137A SBO/F5L19 COE/Cydol 100/20   100 71 JP.105.198 SBO/F5L19 COE/Cydol 200/20   100 72

COE, NBM, and NBE readily participate in ROCM reactions as indicated by their increased viscosity measurements and do not have an inhibitory effect on the metathesis catalyst.

Example 9

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using SBO as olefinic substrate and CDDE, NBE and Cyclol as the cyclic olefins. The results are provided in Table 8. TABLE 8 Ring opening cross metathesis of SBO and CDDE Cyclic Seed Oil/ Olefin C827 Conv. Viscosity Reaction # Batch # Cyclic Olefin mol % (ppm) (%) (cP)a JP.125.025 SBO/F5J26 CDDE/NBE  50/10 100 67 JP.125.019 SBO/F5J26 CDDE/NBE 100/20 100 68 JP.125.020 SBO/F5J26 CDDE/NBE 200/20 200 74 JP.105.193 SBO/F5L19 CDDE/Cydol  50/10 100 68 JP.105.194 SBO/F5L19 CDDE/Cydol 100/10 200 68 JP.105.195 SBO/F5L19 CDDE/Cydol 100/20 200 73 JP.105.197 SBO/F5L19 CDDE/Cydol 200/20 200 75 800

CDDE readily participate in ROCM reactions as indicated by its increased viscosity measurement and does not have an inhibitory effect on the metathesis catalyst.

Example 10

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO as olefinic substrate and DCPD, NBM, NBE and Cyclol as cyclic olefins. The results are provided in Table 9. TABLE 9 Ring insertion cross metathesis of SBO and DCPD Cyclic Seed Oil/ Olefin C827 Conv. Reaction # Batch # Cyclic Olefin mol % (ppm) (%) JP.105.150 SBO/F5L19 DCPD/NBM   10/1.0 50 63 JP.105.151 SBO/F5L19 DCPD/NBM   10/1.0 100 69 JP.125.056 SBO/F6C13 DCPD/NBM  50/10 100 65 JP.125.057 SBO/F6C13 DCPD/NBM 100/10 100 68 JP.125.058 SBO/F6C13 DCPD/NBM 100/20 200 67 JP.125.059 SBO/F6C13 DCPD/NBM 200/20 300 67 JP.105.180 SBO/F5L19 DCPD/NBE   10/1.0 100 68 JP.105.181 SBO/F5L19 DCPD/NBE   20/1.0 100 68 JP.125.001 SBO/F5J26 DCPD/NBE  50/10 100 68 JP.125.002 SBO/F5J26 DCPD/NBE 100/10 200 68 JP.125.003 SBO/F5J26 DCPD/NBE 100/20 200 67 JP.125.004 SBO/F5J26 DCPD/NBE 200/20 300 68 JP.105.177 SBO/F5L19 DCPD/Cydol   10/1.0 100 68 JP.105.178 SBO/F5L19 DCPD/Cydol   20/1.0 100 67 JP.105.188 SBO/F5L19 DCPD/Cydol 50/5 100 67 JP.105.189 SBO/F5L19 DCPD/Cydol  50/10 100 69 JP.105.191 SBO/F5L19 DCPD/Cydol 100/10 200 71 JP.105.192 SBO/F5L19 DCPD/Cydol 100/20 200 69 JP.105.207 SBO/F5J26 DCPD/Cydol 200/20 400 73

DCPD, NBE, NBM and Cyclol do not have an inhibitory effect on the metathesis catalyst.

Example 11

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using SBO/F5J26 as olefinic substrate and CDTE, NBE and Cyclol as olefinic substrates. The results are provided in Table 10. TABLE 10 Ring insertion cross metathesis of SBO and CDTE Cyclic Olefin C827 Conv. Reaction # Cyclic Olefin mol % (ppm) (%) JP.125.007 CDTE/NBE 100/20 200 74 JP.125.008 CDTE/NBE 200/20 400 75 JP.125.009 CDTE/Cydol  50/10 100 71 JP.125.010 CDTE/Cydol 100/10 200 74 JP.125.011 CDTE/Cydol 100/20 200 74 JP.125.012 CDTE/Cydol 200/20 300 75

CDTE, NBE and Cyclol do not have an inhibitory effect on the metathesis catalyst.

Example 12

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using lights removed metathesized soybean oil (RMSBO) as olefinic substrate and various cyclic olefins. The results are provided in Table 11.

RMSBO is produced by metathesizing SBO to 68% conversion, then removing the lights under high vacuum while heating to 200° C. This process removes ˜8 wt % of light hydrocarbons from the reaction. TABLE 11 Ring opening cross metathesis of RMSBO and Cyclic Olefins Ratio of Cyclic Olefin C827 Conv. Product 9C₁₅ ester to Reaction # Cyclic Olefin mol % (ppm) (%) a Solid^(a) palmitate^(b) RLP 66-084 none 0 50 68 no 1.40 CWL81-133 COE/NBM   10/1.0 50 67 JP.125.068 COE/NBM  50/10 100 66 0.72 JP.125.069 COE/NBM 100/10 100 71 Y (clear elastic) 0.44 JP.125.070 COE/NBM 100/20 200 73 0.40 JP.125.071 COE/NBM 200/20 300 73 Y (clear elastic) 0.38 CWL81-130 COE/NBE   10/1.0 50 66 JP.125.072 COE/NBE  50/10 100 71 0.57 JP.125.087 COE/NBE 100/5  100 72 0.42 JP.125.073^(c) COE/NBE 100/10 100 74 0.43 JP.125.074 COE/NBE 100/20 200 72 0.39 JP.125.075 COE/NBE 200/20 300 73 0.29 JP.105.200 COE/Cydol 100/5  200 70 Y (elastic) 0.47 JP.105.201 COE/Cydol  50/10 200 67 0.87 JP.105.202 COE/Cydol 100/20 200 70 Y (elastic) 0.62 JP.105.203 COE/Cydol 200/20 200 72 Y (elastic) 0.44 JP.125.129 CDDE/NBE  50/10 100 70 0.95 JP.125.130 CDDE/NBE 100/10 100 69 0.89 JP.125.131 CDDE/NBE 100/20 200 72 0.70 JP.125.132 CDDE/NBE 200/20 400 76 0.41 JP.125.088 DCPD/NBE 100/5  100 72 1.39 JP.125.080 DCPD/NBE  50/10 100  92? 1.23 JP.125.081 DCPD/NBE 100/10 200 69 1.41 JP.125.082 DCPD/NBE 100/20 300 71 0.97 JP.125.083 DCPD/NBE 200/20 400 69 Y (white wax) 1.27 JP.125.089 DCPD/Cydol 100/5  200 69 1.02 JP.125.076 DCPD/Cydol  50/10 100  85? 0.53 JP.125.077 DCPD/Cydol 100/10 200 69 1.36 JP.125.078 DCPD/Cydol 100/20 300 68 1.21 JP.125.079 DCPD/Cydol 200/20 400 70 Y (white wax) 1.16 ^(a)Metathesis product was a solid or precipitated. ^(b)Ratio of 9C15ester to palmitate uses palmitate as an internal standard to determine the conversion of SBO to ROCM products. The 9C15 ester is consistently produced in SBO metathesis reactions. Plamitate is inert to metathesis and is easy intergrate by GC, therefore it is an ideal internal standard in these SBO metathesis reactions. ^(c)Viscosity of sample was 14300 cP

COE, NBM, NBE, Cyclol and DCPD do not have an inhibitory effect on the metathesis catalyst. The decrease in the 9C15 ester to palmitate ratio indicates that the cyclic olefins are ring opening cross metathesizing with SBO to form new products.

Example 13

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using castor oil as olefinic substrate and HNB, BNB, COE, DCPD and CDDE as cyclic olefins. The results are provided in Table 12. TABLE 12 Ring opening cross metathesis of Caster Oil and Cyclic Olefins Cyclic Cyclic Olefin C827 Conv. Reaction # Olefin mol % (ppm) (%) JP.105.139 HNB 20 200 58 JP.105.140 HNB 20 400 57 JP.125.037 BNB 50 200 58 JP.125.038 BNB 100 200 59 JP.125.039 BNB 200 400 58 JP.105.133 COE 5 100 46 JP.105.134 COE 5 200 55 JP.105.136 COE 10 100 46 JP.105.135 COE 10 200 56 CWL81-115A COE 20 100 42 CWL81-115B COE 20 200 58 CWL81-115C COE 20 400 59 JP.125.035 COE 50 200 62 JP.105.163 COE 100 200 62 JP.105.164 COE 200 400 75 JP.105.144 DCPD 10 200 61 JP.105.145 DCPD 20 400 59 JP.125.032 DCPD 50 200 56 JP.125.033 DCPD 100 200 54 JP.125.034 DCPD 200 400 43 CWL81-117C CDDE 10 200 53 CWL81-117A CDDE 20 200 56 CWL81-117B CDDE 20 400 59 CWL81-142 none N/A 200 58

HNB, BNB, COE, DCPD and CDDE do not have an inhibitory effect on the metathesis catalyst.

Example 14

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using SBO/F5J26 as olefinic substrate and COE, CDDE, DCPD, CDTE and ENB as cyclic olefins. The results are provided in Table 13. TABLE 13 Ring insertion cross metathesis of SBO and Cyclic Olefins Cyclic Cyclic Olefin Conv. Reaction # Olefin mol % C827 (ppm) (%) JU-108-046 COE 20 50 66 JU-108-047 COE 50 50 67 JU-108-048 COE 100 100 71 JU-108-049 COE 200 100 68 JU-108-056 CDDE 5 50 66 JU-108-057 CDDE 10 50 64 JU-108-058 CDDE 20 50 72 JU-108-059 CDDE 50 50 63 JU-108-060 CDDE 100 100 68 JU-108-061 CDDE 200 100 67 JU-108-062 DCPD 5 50 67 JU-108-063 DCPD 10 50 76 JU-108-064 DCPD 20 50 72 JU-108-065 DCPD 50 50 72 JU-108-066 DCPD 100 100 69 JU-108-067 DCPD 200 100 69 JU-108-050 CDTE 5 50 68 JU-108-051 CDTE 10 50 68 JU-108-052 CDTE 20 50 69 JU-108-053 CDTE 50 50 66 JU-108-054 CDTE 100 100 73 JU-108-055 CDTE 200 100 75 JU-108-090 ENB 20 50 73 JU-108-091 ENB 50 50 82 JU-108-092 ENB 100 100 74 JU-108-093 ENB 200 100 78 COE, CDDE, DCPD, CDTE and ENB do not have any inhibitory effect on the metathesis catalyst.

Example 15

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using RMSBO as olefinic substrate and COE, CDDE, DCPD, CDTE and ENB as cyclic olefins. The results are provided in Table 14. TABLE 14 Ring insertion cross metathesis of RMSBO and Cyclic Olefins Ratio Cyclic of 9C15 Cyclic Olefin C827 Conv. Product ester to Reaction # Olefin mol % (ppm) (%) a Solid^(a) palmitate RLP 66-084 none 0 50 68 No 1.40 JU-108-044 COE 5 50 66 1.16 JU-108-045 COE 10 50 66 1.08 JU-108-068 COE 20 50 77 0.59 JU-108-069 COE 50 50 73 0.51 JU-108-070 COE 100 100 solid Y JU-108-071 COE 200 100 solid Y JU-108-094 CDDE 50 50 — JU-108-095 CDDE 100 100 73 0.42 JU-108-096 CDDE 200 100 73 Y 0.34 JU-108-078 DCPD 5 50 76 0.81 JU-108-079 DCPD 10 50 73 0.78 JU-108-080 DCPD 20 50 73 0.59 JU-108-081 DCPD 50 50 68 JU-108-082 DCPD 100 100 72 JU-108-083 DCPD 200 100 solid Y JU-108-072 CDTE 5 50 71 0.66 JU-108-073 CDTE 10 50 71 0.64 JU-108-074 CDTE 20 50 72 0.55 JU-108-075 CDTE 50 50 69 0.49 JU-108-076 CDTE 100 100 solid Y JU-108-077 CDTE 200 100 solid Y JU-108-084 ENB 5 50 79 0.74 JU-108-085 ENB 10 50 75 0.70 JU-108-086 ENB 20 50 76 0.73 JU-108-087 ENB 50 50 77 0.70 JU-108-088 ENB 100 100 74 1.06 JU-108-089 ENB 200 100 81 1.08 ^(a)Metathesis product was a solid or precipitated.

COE, CDDE, DCPD, CDTE and ENB do not have an inhibitory effect on the metathesis catalyst. The decrease in the 9C15 ester to palmitate ratio indicates that the cyclic olefins are ring opening cross metathesizing with SBO to form new products.

Example 16

Ring opening cross metathesis was carried out according to the General Metathesis Procedure using various olefinic substrates and cyclic olefins. The results are provided in Table 15. TABLE 15 Ring insertion cross metathesis of SBO (batch F5L19) or RMSBO with Cyclic Olefins Seed Cyclic Cyclic Olefin C827 Conv. Reaction # Oil Olefin mol % (ppm) (%) Solidified^(a) JU-108-042 SBO COE 5 50 69 JU-108-043 SBO COE 10 50 69 JU-108-046 SBO COE 20 50 66 JU-108-047 SBO COE 50 50 67 JU-108-048 SBO COE 100 100  71 JU-108-049 SBO COE 200 100  68 JU-108-056 SBO CDDE 5 50 66 JU-108-057 SBO CDDE 10 50 64 JU-108-058 SBO CDDE 20 50 72 JU-108-059 SBO CDDE 50 50 63 JU-108-062 SBO DCPD 5 50 67 JU-108-063 SBO DCPD 10 50 76 JU-108-064 SBO DCPD 20 50 72 JU-108-065 SBO DCPD 50 50 72 JU-108-066 SBO DCPD 100 100  69 JU-108-067 SBO DCPD 200 100  69 JU-108-050 SBO CDTE 5 50 68 JU-108-051 SBO CDTE 10 50 68 JU-108-052 SBO CDTE 20 50 69 JU-108-053 SBO CDTE 50 50 66 JU-108-054 SBO CDTE 100 100  73 JU-108-055 SBO CDTE 200 100  75 JU-108-044 RMSBO COE 5 50 66 JU-108-045 RMSBO COE 10 50 66 JU-108-068 RMSBO COE 20 50 77 JU-108-069 RMSBO COE 50 50 73 JU-108-070 RMSBO COE 100 100  — Yes^(b) JU-108-071 RMSBO COE 200 100  — Yes^(b) JU-108-072 RMSBO CDTE 5 50 71 JU-108-073 RMSBO CDTE 10 50 71 JU-108-074 RMSBO CDTE 20 50 72 JU-108-075 RMSBO CDTE 50 50 69 JU-108-076 RMSBO CDTE 100 100  — Yes^(b) JU-108-077 RMSBO CDTE 200 100  — Yes^(b) JU-108-078 RMSBO DCPD 5 50 76 JU-108-079 RMSBO DCPD 10 50 73 JU-108-080 RMSBO DCPD 20 50 73 JU-108-081 RMSBO DCPD 50 50 68 JU-108-082 RMSBO DCPD 100 100  72 No^(c) JU-108-083 RMSBO DCPD 200 100  — Yes^(c) CWL-81- MO COD 100  50^(d) 29 100 monoxide JP-105.086 SBO COD 100 450  10 monoxide ^(a)Metathesis product was a solid or precipitated. ^(b)Clear jelly. ^(c)White, opaque. ^(d)Catalyst 627 used

COE, CDDE, DCPD, and CDTE do not have an inhibitory effect on the metathesis catalyst. COD monoxide has an inhibitory effect on metathesis catalysts 827 and 627.

Example 17

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using various seed oils and COE as cyclic olefin. The results are provided in Table 16. TABLE 16 Ring insertion cross metathesis of Seed Oils with COE Cyclic Olefin C827 Conv. at 2 hr Conv. at Lot # Seed Oil mol % (ppm) (%) 17 hr (%) Solidified^(a) JP.125.146 Canola 80 730 70 68 JP.125.147 Corn 79 740 75 75 JP.125.148 Peanut 80 740 63 65 JP.125.149 Safflower 80 740 84 83 JP.125.150 Olive 80 740 60 61 JP.125.151 Jojoba 55 510 75 Y JP.125.152 Meadowfoam 85 790 79 79 Y ^(a)Metathesis product was a solid or precipitated.

All of the seed oils in Table 16 and COE are substrates for ROCM reactions.

Example 18

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using SBO/F6C13 as olefinic substrate, COE (100 mol %) as cyclic olefin, and various metathesis catalysts. The results are provided in Table 17. TABLE 17 Ring insertion cross metathesis of SBO and Cyclooctene^(a) with various catalysts Catalyst Metathesis Loading Conv. at 2 hr Conv. at 18 hr Entry Lot # Catalyst (ppm) (%) (%) 1 JP.125.136 823 1000 N/D 51 2 JP.125.137 601 1000 N/D 38 3 JP.125.138 801 1000 N/D 40 4 JP.125.139 838 1000 N/D 15 5 JP.125.140 701 1000 N/D 36 6 JP.125.141 848 500 68 72 7 JP.125.142 627 500 75 74 8 JP.125.143 697 500 27 29 9 JP.125.144 933 500 72 73 10 JP.125.145 712 500 74 74 ^(a)1 mol of COE per 1 mol of SBO.

This data shows that a wide variety of metathesis catalysts will metathesize seed oil ROCM reactions.

Example 19

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using a chain transfer agent with a seed oil and a cyclic olefin using 827 metathesis catalyst. The results are provided in Table 18.

The goals of these experiments were to develop reaction conditions that yielded cyclic olefin inserted products that were terminated by the chain transfer agent. Percent Conversion (% Convers.) is defined as the percent of substrate that has been converted to another metathesis product (ie 66% conversion represents new metathesis products with 34% unreacted substrate). TABLE 18 ROCM reactions with a chain transfer agent. Chain Cyclic transfer Phase at Reaction # Substrate^(a) Olefin^(a) agent^(a) 827 (ppm) 25° C. % Conv. JP.140.057A SBO (1) COE (3) 9C18DE (3) 2100 liquid — JP.140.057B SBO (1) COE (6) 9C18DE (3) 2700 liquid JP.140.057C SBO (1) COE (9) 9C18DE (3) 3300 liquid JP.140.057D SBO (1) COE (15) 9C18DE (3) 3900 solid JP.140.057E SBO (1) COE (20) 9C18DE (3) 5500 solid JP.140.061A 9C18DE (1) COE (2) VNB (2) 1000 liquid JP.140.061B 9C18DE (1) COE (4) VNB (2) 1400 liquid JP.140.061C 9C18DE (1) COE (6) VNB (2) 1800 solid JP.140.061D 9C18DE (1) COE (8) VNB (2) 2200 solid JP.140.061E 9C18DE (1) COE (10) VNB (2) 2600 solid JP.140.067A Biodiesel (1) COE (1) BisTMS (1) 1200 liquid 66 JP.140.067B Biodiesel (1) COE (2) BisTMS (1) 1500 liquid 36 JP.140.067C Biodiesel (1) COE (3) BisTMS (1) 1800 liquid 39 JP.140.067D Biodiesel (1) COE (5) BisTMS (1) 2400 liquid 47 JP.140.067E Biodiesel (1) COE (10) BisTMS (1) 3900 liquid 40 JP.140.069A1 SBO (1)^(b) COE (4.5) BisTMS (3)^(b) 3600 liquid — JP.140.069A2 SBO (1)^(b) COE (9) BisTMS (3)^(b) 4950 liquid JP.140.069A3 SBO (1)^(b) COE (13.5) BisTMS (3)^(b) 6300 liquid JP.140.069A4 SBO (1)^(b) COE (22.5) BisTMS (3)^(b) 9000 liquid JP.140.069A5 SBO (1)^(b) COE (45) BisTMS (3)^(b) 15750 liquid JP.140.069B1 SBO (1) COE (4.5) BisTMS (3) 3600 liquid JP.140.069B2 SBO (1) COE (9) BisTMS (3) 4950 liquid JP.140.069B3 SBO (1) COE (13.5) BisTMS (3) 6300 solid/liquid JP.140.069B4 SBO (1) COE (22.5) BisTMS (3) 9000 solid JP.140.069B5 SBO (1) COE (45) BisTMS (3) 15750 solid JP.140.070A SBO (1) COD (2.25) BisTMS (4.5) 2025 liquid JP.140.070B SBO (1) COD (4.5) BisTMS (4.5) 2625 liquid JP.140.070C SBO (1) COD (6.75) BisTMS (4.5) 4725 liquid JP.140.070D SBO (1) COD BisTMS (4.5) 6375 liquid (11.25) JP.140.070E SBO (1) COD (22.5) BisTMS (4.5) 9450 liquid JP.140.071A Biodiesel (1) COD (0.5) BisTMS (1) 1050 liquid JP.140.071B Biodiesel (1) COD (1) BisTMS (1) 1200 liquid JP.140.071C Biodiesel (1) COD (1.5) BisTMS (1) 1350 liquid JP.140.071D Biodiesel (1) COD (2.5) BisTMS (1) 1650 liquid JP.140.071E Biodiesel (1) COD (5) BisTMS (1) 2400 liquid JP.140.073 Biodiesel (1) — BisTMS (1) 900 N/A 55 JP.140.076A1 Biodiesel (1) COE (1) BisTMS (1) 1200 liquid 95 JP.140.076A2 Biodiesel (1) COE (2) BisTMS (1) 1500 liquid 96 JP.140.076A3 Biodiesel (1) COE (3) BisTMS (1) 1800 liquid 97 JP.140.076A4 Biodiesel (1) COE (5) BisTMS (1) 2400 liquid/solid 98 JP.140.076A5 Biodiesel (1) COE (10) BisTMS (1) 3900 solid 99 JP.140.076B1 Biodiesel (1) COD (0.5) BisTMS (1) 1050 liquid 95 JP.140.076B2 Biodiesel (1) COD (1) BisTMS (1) 1200 liquid 95 JP.140.076B3 Biodiesel (1) COD (1.5) BisTMS (1) 1350 liquid 95 JP.140.076B4 Biodiesel (1) COD (2.5) BisTMS (1) 1650 liquid 96 JP.140.076B5 Biodiesel (1) COD (5) BisTMS (1) 2400 liquid 98 JP.140.082 Biodiesel (1) — BisTMS (1) 900 liquid 88 ^(a)mole equivalents ^(b)reacted chain transfer agent with substrate, then added cyclic olefin

ROCM was accomplished using cyclic olefins with a chain transfer agent to produce novel metathesis products as determined by GC analysis and some of the products being solids.

Example 20

General procedure for the cross-metatheses of olefinic substrate and 1-butene: Terminal olefins were synthesized by the cross metathesis 1-butene and seed oils with a ruthenium metathesis catalyst. Seed oils include triacylglycerides, as in soybean oil, fatty acid esters, as in jojoba oil and FAMES, such as methyl esters of soybean oil (soy FAME).

1-Butene used was added to a Fisher-Porter bottle equipped with a stir bar and charged with the olefinic substrates. A solution of olefin metathesis catalyst of an appropriate concentration was prepared in anhydrous dichloromethane (obtained from Aldrich and degassed with Argon) and the desired volume of this solution added to the olefinic substrate. The head of the Fisher-Porter bottle was equipped with a pressure gauge and a dip-tube was adapted on the bottle. The system was sealed and taken out of the glove, box to a gas line. The vessel was then purged 3 times with 1-propene, pressurized to the indicated pressure (about 50 to about 150 psi for 1-propene) and placed in an oil bath at the indicated temperature. The reaction was monitored by GC analysis. The vial was sealed with a Teflon-seal cap and the olefinic substrate/alpha-olefin mixture was brought to the indicated temperature, so that the reactions are conducted under a slightly positive pressure (from 1.1 to about 2 atm, i.e. from 16 psi to about 30 psi). A solution of olefin metathesis catalyst of an appropriate concentration was prepared in anhydrous dichloromethane (obtained from Aldrich and degassed with Ar) and the desired volume of this solution added to the olefinic substrate/alpha-olefin mixture via syringe through the Teflon-seal while stirring. The reaction mixture was kept at the desired temperature for the indicated period of time before adding a 1.0 M solution of THMP (1 mL) via syringe through the Teflon-seal cap. The mixture was then heated at 60° C. for 1 hour, diluted with 5 mL of distilled water and 5 mL of hexanes and the organic phase was separated and analyzed by GC. If the olefinic substrate is a glyceride, it is transesterified to the methyl ester prior to GC analysis.

Propenolyzed Soybean oil (PSBO): To the metathesis catalyst removed product from above was added to a vacuum distillation setup. The pot was heated to 150° C. under high vacuum to remove volatiles. The pot was cooled to room temp and the propenoylzed SBO was used without further purification.

Ring insertion cross metathesis was carried out according to the General Metathesis Procedure using PSBO, a cyclic olefin and a chain using 827 metathesis catalyst loading. The results are provided in Table 19. TABLE 19 ROCM reactions with PSBO, a cyclic olefin and a chain transfer agent. Chain Phase at Cyclic Transfer 25° C. after Reaction # Seed Oil Olefin Agent 827 (ppm) Work up % Conv JP.140.085A PSBO (1) — BisTBS (2) 1500 liquid 71 JP.140.085B PSBO (1) — BisTBS (10) 3900 liquid/ppt 90 JP.140.085C PSBO (1) COE (2) BisTBS (2) 2100 liquid 85 JP.140.085D PSBO (1) COD (1) BisTBS (2) 2100 liquid 85 JP.140.085E PSBO (1) COD (2) BisTBS (2) 2100 liquid/ppt 93 JP.140.085F PSBO (1) COE (4) — 2100 very visc 71 JP.140.085G PSBO (1) COD (2) — 2100 very visc 89 JP.140.085H PSBO (1) COD (4) — 2100 solid 81 JP.140.086A A — — liquid 71 JP.140.086C B — — — liquid 85 JP.140.086D C — — — liquid 85 JP.140.087^(a) PSBO (1) COE (4) — 2100 liquid 73 JP.140.088^(b) PSBO (1) — BisTBS (10) 3900 liquid 94 JP.140.090 PSBO (1) COE (2) BisTBS (2) 2100 ND 96 JP.140.091 PSBO (1) COE (2) BisTBS (2) 2100 ND 94 JP.140.089 9DA (1) COE (2) BisTBS (1) 1200 ND — JP.140.092 9DA (1) COD (2) BisTBS (1) 1500 ND — JP.140.098A PSBO (1) COE (2) — 100 ND 74 JP.140.098B PSBO (1) COE (2) — 200 ND 74 JP.140.098C PSBO (1) COE (2) — 400 ND 74 JP.140.098D PSBO (1) COD (2) — 140 ND 83 JP.140.098E PSBO (1) COD (2) — 280 ND 83 JP.140.098F PSBO (1) COD (2) — 560 ND 83 JP.140.099 PSBO (1) COD (2) — 2100 ND 83 JP.140.100 PSBO (1) COE (2) — 1500 ND 75 JP.140.105A PSBO (1) COE (2) — 50 ND 68 JP.140.105B PSBO (1) COE (2) — 125 ND 70 JP.140.105C PSBO (1) COE (2) — 150 ND 69 JP.140.105D PSBO (1) COD (2) — 70 ND 79 JP.140.105E PSBO (1) COD (2) — 175 ND 79 JP.140.105F PSBO (1) COD (2) — 210 ND 83 A = Deprotected product from JP.140.085A which was reanalyzed B = Deprotected product from JP.140.085C which was reanalyzed C = Deprotected product from JP.140.085D which was reanalyzed ^(a)Scale Up of JP.140.085F ^(b)Repeated JP.140.085B

Propenolyzed soybean oil is a good substrate for ROCM reactions with cyclic olefins and a chain transfer agent. Good to high conversions were obtained in the reactions.

Example 21

Table 20 Contains GPC data for numerous ROCM reactions. The goal of this study was to understand the reaction conditions that would produce the desired ROCM products. TABLE 20 GPC Data for ROCM Reactions using 827 metathesis catalysts. Equiv of Cyclic Olefins to Mn Mw MP PDI* Cyclic Substrate 827 Conv (Major Peak vs. PSS Notebook # Substrate Olefin (mol/mol) (ppm) (%) reported in Daltons) JP.140.009D 9C18 COE 5 1000 85 2845 3645 3294 1.28 JP.140.024A 9C18 COE 10 1800 90 4072 6441 7368 1.58 JP.140.024C 9C18 COE 20 3500 96 8578 15840 15518 1.85 JP.140.010E 9C18DE COE 10 1800 90 2924 4487 3923 1.53 JP.140.025B 9C18DE COE 15 2700 94 5685 8504 8712 1.5 JP.140.025C 9C18DE COE 20 3500 96 7165 11265 11511 1.57 JP.140.027A MO COE 10 1800 84 3713 5922 6953 1.6 JP.140.027B MO COE 15 2700 95 6187 9219 9292 1.49 JP.140.027C MO COE 20 3500 96 6005 10416 11470 1.73 JP.140.028A CF COE 10 1800 80 4298 6258 6656 1.46 JP.140.028B CF COE 15 2700 87 6029 9057 9241 1.5 JP.140.028C CF COE 20 3500 90 7650 11677 12157 1.53 JP.140.021F Castor Oil COE 20 2000 84 5643 11222 21449 1.99 JP.140.033A1 9C18 COE 5 1000 99 2581 3137 2786 1.22 JP.140.033A2 9C18 COE 10 1800 98 3295 4964 5513 1.51 JP.140.033A3 9C18 COE 20 3500 99 5426 9130 9954 1.68 JP.140.033B1 9C18DE COE 10 1800 NYD 2735 4084 3796 1.49 JP.140.033B2 9C18DE COE 15 2700 NYD 3738 5896 6710 1.58 JP.140.033B3 9C18DE COE 20 3500 NYD 4630 7651 8454 1.65 JP.140.033C1 MO COE 10 1800 99 2949 4263 4125 1.45 JP.140.033C2 MO COE 15 2700 99 3970 6377 6921 1.61 JP.140.033C3 MO COE 20 3500 99 5025 9242 9495 1.84 JP.140.039A Castor — — — — 40 68 64 1.68 FAME JP.140.012A CF COE 0.5 1000 42 38 79 77 2.07 JP.125.206A CF COE 1 1000 48 1239 1293 1059 1.05 JP.140.012B CF COE 2 1000 69 1711 1859 1322 1.09 JP.140.012C CF COE 3 1000 75 1879 2147 1758 1.14 JP.140.012D CF COE 5 1000 84 2021 2537 2367 1.25 JP.140.033D1 CF COE 10 1800 99 3089 4804 5601 1.55 JP.140.033D2 CF COE 15 2700 99 4050 6720 7267 1.66 JP.140.033D3 CF COE 20 3500 99 5852 9607 10030 1.64 JP.140.039B Castor Oil — — — — 1442 1459 1486 1.01 JP.140.036A Castor Oil — — 600 ND 11896 17024 31181 1.43 JP.140.036B Castor Oil COE 3 1200 ND 5345 8439 11887 1.58 JP.140.036C Castor Oil COE 9 2400 ND 3980 7707 13390 1.94 JP.140.036D Castor Oil COE 15 3600 ND 5141 8773 14238 1.71 JP.140.044 Castor Oil COE 20 4600 ND 8235 24287 54459 2.95 JP.140.033E Castor Oil COE 20 2000 ND 5563 18050 38940 3.24 JP.140.036E Castor Oil COE 30 6600 ND 8237 17364 32816 2.11 JP.140.039C — COE — — — 75 90 94 1.19 JP.140.003 — COE — 1000 — 4910 9626 7393 1.96 JP.140.039D C12 — — — — 65 JP.140.037A MO COD 1 600 91 44 397 86 8.98 JP.140.037B MO COD 5 1100 98 1187 2044 2196 1.72 JP.140.037C MO COD 10 2100 99 2752 3751 3725 1.36 JP.140.037D CF COD 1 600 66 523 719 286 1.37 JP.140.037E CF COD 5 1100 90 1849 2288 2201 1.25 JP.140.037F CF COD 10 2100 95 2642 3705 4010 1.4 JP.140.038A MO PBD 1 600 92 72 189 45 2.6 JP.140.038B MO PBD 5 1100 91 212 754 488 3.56 JP.140.038C MO PBD 10 2100 97 600 1350 1327 2.25 JP.140.038D CF PBD 1 600 54 28 187 29 6.59 JP.140.038E CF PBD 5 1100 76 541 945 568 1.75 JP.140.038F CF PBD 10 2100 92 582 1322 1368 2.27 JP.140.041A1 Castor Oil COD 3 1800 ND 4262 7773 12212 1.82 JP.140.041B1 Castor Oil COD 9 4200 ND 6309 11466 18572 1.82 JP.140.041C1 Castor Oil COD 15 6600 ND 4479 10619 20058 2.37 JP.140.041D1 Castor Oil COD 20 8600 ND 4022 10055 20165 2.5 JP.140.041E1 Castor Oil COD 30 12600 ND 6286 12014 21854 1.91 JP.140.041A2 Castor Oil PBD 3 1200 ND 3619 8122 7641 2.24 JP.140.041B2 Castor Oil PBD 9 2400 ND 5134 11159 9756 2.17 JP.140.041C2 Castor Oil PBD 15 3600 ND 5695 11684 10560 2.05 JP.140.041D2 Castor Oil PBD 20 4600 ND 2200 7417 8214 3.37 JP.140.041E2 Castor Oil PBD 30 6600 ND 2108 6933 7776 3.29 JP.140.043A 9C18 — — ND 338 340 338 1 JP.140.043B 9C18DE — — ND 421 424 425 1.01 JP.140.043C MO — — ND 382 387 381 1.01 JP.140.043D MO — 200 ND 381 386 383 1.01 JP.140.043E — PBD — — ND 4938 8145 7320 1.65 JP.140.043F — PBD — 200 ND 3379 8523 8020 2.52 JP.140.043G — COD — — ND 490 493 500 1.01 JP.140.043H — COD — 400 ND 34375 45119 53596 1.31 JP.140.043I SBO — — ND 1260 1270 1283 1.01 JP.140.043J SBO — 900 ND 7711 10422 6108 1.35 JP.140.045 CF — — 200 ND 528 537 540 1.02 JP.140.042 Castor Oil COD 30 12600 ND 9769 30449 73647 3.12

The data demonstrate that numerous acyclic olefins can be run under ROCM reaction conditions to produce the desired high molecular weight products. Many of the products have good PDIs ranging from 1 to 2, which represent products that are useful in industrial applications. 

1. A method for carrying out a catalytic ring-opening cross-metathesis reaction, comprising contacting (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol, with (b) at least one cyclic olefin as a cross metathesis partner, in the presence of (c) a ruthenium alkylidene olefin metathesis catalyst, (d) under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate.
 2. The method of claim 1, wherein the olefinic substrate is an esterification product of an unsaturated fatty acid with an alcohol.
 3. The method of claim 2, wherein the alcohol is a saturated alcohol.
 4. The method of claim 3, wherein the saturated alcohol is monohydric.
 5. The method of claim 3, wherein the saturated alcohol is dihydric or polyhydric.
 6. The method of claim 5, wherein the saturated alcohol is selected from 1,2-dihydroxypropane and glycerol.
 7. The method of claim 2, wherein the at least one olefinic substrate comprises a monoglyceride, a diglyceride, a triglyceride, or a mixture thereof.
 8. The method of claim 2, wherein the olefinic substrate comprises a seed oil.
 9. The method of claim 7, wherein the olefinic substrate has the structure of formula (I)

wherein R^(V), R^(VI), and R^(VII) are independently selected from hydrogen, C₁ to C₃₆ hydrocarbyl, C₁ to C₃₆ substituted hydrocarbyl, C₁ to C₃₆ heteroatom-containing hydrocarbyl, C₁ to C₃₆ substituted heteroatom-containing hydrocarbyl, and functional groups, provided that at least one of R^(V), R^(VI), and R^(VII) is other than hydrogen and comprises an internal olefin.
 10. The method of claim 9, wherein R^(V), R^(VI), and R^(VII) are independently selected from C₁ to C₁₅ alkylene.
 11. The method of claim 10, wherein R^(V), R^(VI), and R^(VII) are independently selected from C₄ to C₁₂ alkylene.
 12. The method of claim 9, wherein each of R^(V), R^(VI), and R^(VII) is C₁ to C₃₆ hydrocarbyl containing zero to two double bonds and optionally substituted with one or two hydroxyl groups.
 13. The method of claim 12, wherein each of R^(V), R^(VI), and R^(VII) is C₁ to C₁₈ hydrocarbyl containing zero to two double bonds and optionally substituted with one or two hydroxyl groups.
 14. The method of claim 1, wherein the cyclic olefin is an optionally substituted, optionally heteroatom-containing, mono-unsaturated, di-unsaturated, or poly-unsaturated C₅ to C₂₄ hydrocarbon.
 15. The method of claim 14, wherein the cyclic olefin is a mono-unsaturated, di-unsaturated, or poly-unsaturated C₆ to C₁₆ hydrocarbon optionally substituted with one or two hydroxyl groups and optionally containing an ester linkage.
 16. The method of claim 15, wherein the cyclic olefin is mono-unsaturated, di-unsaturated, or tri-unsaturated.
 17. The method of claim 16, wherein the cyclic olefin is mono-unsaturated.
 18. The method of claim 1, wherein the at least one cyclic olefin is a mixture of a cyclic olefinic hydrocarbon and a cyclic alkenol.
 19. The method of claim 1, wherein the molar ratio of the olefinic substrate to the cyclic olefin is in the range of about 1:2 to about 1:10000.
 20. The method of claim 19, wherein the molar ratio of the olefinic substrate to the cyclic olefin is in the range of about 1:5 to about 1:1000.
 21. The method of claim 18, wherein the olefinic substrate, the cyclic olefinic hydrocarbon, and the cyclic alkenol are in a ratio of approximately 1:50:50.
 22. The method of claim 18, wherein the molar ratio of the cyclic olefinic hydrocarbon to the cyclic alkenol is in the range of about 1:1 to about 1:100.
 23. The method of claim 22, wherein the molar ratio of the cyclic olefinic hydrocarbon to the cyclic alkenol is in the range of about 1:1 to about 1:10.
 24. The method of claim 18, wherein the molar ratio of the cyclic olefinic hydrocarbon to the cyclic alkenol is in the range of about 100:1 to about 1:1
 25. The method of claim 24, wherein the molar ratio of the cyclic olefinic hydrocarbon to the cyclic alkenol is in the range of about 10:1 to about 1:1.
 26. The method of claim 1, wherein the contacting is carried out in an inert atmosphere.
 27. The method of claim 1, wherein the contacting is carried out in an oxygen-containing atmosphere.
 28. The method of claim 1, wherein the catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate.
 29. The method of claim 28, wherein the catalyst is present in an amount ranging from about 50 ppm to about 300 ppm relative to the olefinic substrate.
 30. The method of claim 1, wherein the ruthenium alkylidene olefin metathesis catalyst has the structure of formula (II)

wherein: M is ruthenium; n is 0 or 1; m is 0, 1, or 2; L¹, L² and L³ are neutral electron donor ligands; X¹ and X² are anionic ligands; and R¹ and R² are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups; wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together to form a cyclic group, and further wherein any one of X¹, X², L¹, L², L³, R¹, and R² can be attached to a support.
 31. The method of claim 30, wherein: n and m are 0; R¹ is hydrogen, and R² is selected from C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and C₅-C₂₀ aryl, optionally substituted with one or more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl; L¹ and L² are independently selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, and thioether; and X¹ and X² are independently selected from hydrogen, halide, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₀ aryloxycarbonyl, C₂-C₂₀ acyl, C₂-C₂₀ acyloxy, C₁-C₂₀ alkylsulfonato, C₅-C₂₀ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, or C₅-C₂₀ arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl.
 32. The method of claim 30, wherein L¹ has the structure of formula (III)

in which: X and Y are heteroatoms selected from N, O, S, and P; p is zero when X is O or S, and p is 1 when X is N or P; q is zero when Y is O or S, and q is 1 when Y is N or P; Q¹, Q², Q³, and Q⁴ are independently selected from hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, substituted heteroatom-containing hydrocarbylene, and —(CO)—, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group; w, x, y, and z are independently zero or 1; and R³, R^(1A), R⁴, and R^(4A) are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, and substituted heteroatom-containing hydrocarbyl, such that the transition metal complex is a ruthenium carbene complex having the structure of formula (IV)

wherein any two or more of X¹, X², L², L¹, R¹, R², R³, R^(3A), R⁴, and R^(4A) can be taken together to form a cyclic group, and further wherein any one or more of X¹, X², L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) may be attached to a support.
 33. The method of claim 32, wherein m, w, x, y, and z are zero, X and Y are N, and R^(3A) and R^(4A) are linked to form -Q-, such that the ruthenium carbene complex has the structure of formula (VI)

wherein Q is a hydrocarbylene, substituted hydrocarbylene, heteroatom-containing hydrocarbylene, or substituted heteroatom-containing hydrocarbylene linker, and further wherein two or more substituents on adjacent atoms within Q may be linked to form an additional cyclic group.
 34. The method of claim 33, wherein Q has the structure —CR¹¹R¹²—CR¹³R¹⁴— or —CR¹¹═CR¹³—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently selected from hydrogen, hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substituted heteroatom-containing hydrocarbyl, and functional groups, and or wherein any two of R¹¹, R¹², R¹³, and R¹⁴ may be linked together to form a substituted or unsubstituted, saturated or unsaturated ring.
 35. The method of claim 34, wherein: R¹ is hydrogen, and R² is selected from C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, and aryl, optionally substituted with one or more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl; L² is selected from phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine, sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine, imidazole, substituted imidazole, pyrazine, and thioether; X¹ and X² are independently selected from hydrogen, halide, C₁-C₂₀ alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₀ aryloxycarbonyl, C₂-C₂₀ acyl, C₂-C₂₀ acyloxy, C₁-C₂₀ alkylsulfonato, C₅-C₂₀ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₀ arylsulfanyl, C₁-C₂₀ alkylsulfinyl, or C₅-C₂₀ arylsulfinyl, any of which, with the exception of hydrogen and halide, are optionally further substituted with one or more groups selected from halide, C₁-C₆ alkyl, C₁-C₆ alkoxy, and phenyl; R³ and R⁴ are aromatic, substituted aromatic, heteroaromatic, substituted heteroaromatic, alicyclic, substituted alicyclic, heteroatom-containing alicyclic, or substituted heteroatom-containing alicyclic, composed of from one to about five rings; and R¹² and R¹⁴ are hydrogen, and R¹¹ and R¹³ are selected from hydrogen, lower alkyl and phenyl, or are linked to form a cyclic group.
 36. The method of claim 1, wherein the catalyst is a Grubbs-Hoveyda complex.
 37. The method of claim 36, wherein the complex has an N-heterocyclic carbene ligand associated with the ruthenium center.
 38. The method of claim 1, wherein the cyclic olefin is functionalized.
 39. A ring-opening cross-methathesis reaction (ROCM) product prepared by the method of any one of claims 1, 7, or
 30. 40. The ROCM product of claim 39, wherein the ROCM product comprises a monomer, dimer, trimer, oligomer, or a mixture thereof.
 41. The ROCM product of claim 40, wherein the ROCM product comprises a chain-extended olefinic substrate.
 42. The ROCM product of claim 41, wherein the chain-extended olefinic substrate comprises a chain-extended glyceride.
 43. The ROCM product of claim 42, wherein the chain-extended glyceride comprises a chain-extended monoglyceride, a chain-extended diglyceride, a chain-extended triglyceride, or a mixture thereof.
 44. A chain-extended olefinic substrate formed by a catalytic ring-opening cross-metathesis reaction, the catalytic ring-opening cross-metathesis reaction comprising contacting (a) at least one olefinic substrate selected from: (i) an unsaturated fatty acid; (ii) an unsaturated fatty alcohol; (iii) an esterification product of an unsaturated fatty acid with an alcohol; and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol, with (b) at least one cyclic olefin as a cross metathesis partner, in the presence of (c) a ruthenium alkylidene olefin metathesis catalyst, under conditions effective to allow ring-insertion cross-metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate to form the chain-extended olefinic substrate.
 45. A method for manufacturing a wax, comprising: (a) contacting at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol, with at least one cyclic olefin as a cross metathesis partner, in the presence of a ruthenium alkylidene olefin metathesis catalyst, under conditions effective to allow ring insertion cross metathesis whereby the cyclic olefin is simultaneously opened and inserted into the olefinic substrate to provide an olefinic product; (b) partially or completely hydrogenating the olefinic product.
 46. A reaction system for carrying out a catalytic ring-opening cross-metathesis reaction comprising: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol; (b) at least one cyclic olefin; and (c) a ruthenium alkylidene olefin metathesis catalyst.
 47. The reaction system of claim 46, wherein the ruthenium alkylidene olefin metathesis catalyst is present in an amount that is less than about 1000 ppm relative to the olefinic substrate.
 48. The reaction system of claim 46, wherein the at least one olefinic substrate comprises a monoglyceride, a diglyceride, a triglyceride, or a mixture thereof.
 49. A reaction system for manufacturing a wax comprising: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol; (b) at least one cyclic olefin; and (c) a ruthenium alkylidene olefin metathesis catalyst.
 50. A kit of parts for carrying out a catalytic ring-opening cross-metathesis reaction, comprising: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol; and (b) a ruthenium alkylidene olefin metathesis catalyst.
 51. The kit of parts of claim 50, further comprising at least one cyclic olefin.
 52. The kit of parts of claim 50, further comprising instructions for adding a cyclic olefin to the at least one olefinic substrate.
 53. The kit of parts of claim 50, wherein the catalyst is present in an amount that is less than 1000 ppm relative to the olefinic substrate.
 54. A kit of parts for manufacturing a wax, comprising: (a) at least one olefinic substrate selected from (i) an unsaturated fatty acid, (ii) an unsaturated fatty alcohol, (iii) an esterification product of an unsaturated fatty acid with an alcohol, and (iv) an esterification product of a saturated fatty acid with an unsaturated alcohol; and (b) a ruthenium alkylidene olefin metathesis catalyst.
 55. The kit of parts of claim 54, further comprising at least one cyclic olefin as a cross metathesis partner.
 56. The kit of parts of claim 54, further comprising instructions for adding a cyclic olefin to the at least one olefinic substrate.
 57. The kit of parts of claim 54, wherein the catalyst is present in an amount that is less than 1000 ppm relative to the olefinic substrate. 